WO2009123678A1 - Nonwovens produced from multicomponent fibers - Google Patents

Nonwovens produced from multicomponent fibers Download PDF

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Publication number
WO2009123678A1
WO2009123678A1 PCT/US2009/001717 US2009001717W WO2009123678A1 WO 2009123678 A1 WO2009123678 A1 WO 2009123678A1 US 2009001717 W US2009001717 W US 2009001717W WO 2009123678 A1 WO2009123678 A1 WO 2009123678A1
Authority
WO
WIPO (PCT)
Prior art keywords
sulfopolyester
water
dispersible
fiber
fibers
Prior art date
Application number
PCT/US2009/001717
Other languages
French (fr)
Inventor
Rakesh Kumar Gupta
Daniel William Klosiewicz
Melvin Glenn Mitchell
Original Assignee
Eastman Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Chemical Company filed Critical Eastman Chemical Company
Priority to ES09727198T priority Critical patent/ES2403114T3/en
Priority to KR1020137017905A priority patent/KR101541627B1/en
Priority to JP2011502934A priority patent/JP2011516740A/en
Priority to CN200980120628.2A priority patent/CN102046860B/en
Priority to DK09727198T priority patent/DK2271797T3/en
Priority to BRPI0909456A priority patent/BRPI0909456A2/en
Priority to KR1020107024652A priority patent/KR101362617B1/en
Priority to EP20090727198 priority patent/EP2271797B1/en
Publication of WO2009123678A1 publication Critical patent/WO2009123678A1/en

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Classifications

    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/08Melt spinning methods
    • D01D5/098Melt spinning methods with simultaneous stretching
    • D01D5/0985Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/28Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30Conjugate filaments; Spinnerette packs therefor
    • D01D5/36Matrix structure; Spinnerette packs therefor
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326Condensation or reaction polymers
    • D04H1/435Polyesters
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825Composite fibres
    • D04H1/43828Composite fibres sheath-core
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825Composite fibres
    • D04H1/4383Composite fibres sea-island
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825Composite fibres
    • D04H1/43832Composite fibres side-by-side
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43835Mixed fibres, e.g. at least two chemically different fibres or fibre blends
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43838Ultrafine fibres, e.g. microfibres
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4391Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/44Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
    • D04H1/46Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
    • D04H1/492Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres by fluid jet
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/56Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10Organic non-cellulose fibres
    • D21H13/20Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10Organic non-cellulose fibres
    • D21H13/20Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/24Polyesters
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36Inorganic fibres or flakes
    • D21H13/38Inorganic fibres or flakes siliceous
    • D21H13/40Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H15/00Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • D21H15/10Composite fibres
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2904Staple length fiber
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2915Rod, strand, filament or fiber including textile, cloth or fabric
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2929Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2929Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • Y10T428/2931Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/298Physical dimension
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/608Including strand or fiber material which is of specific structural definition
    • Y10T442/609Cross-sectional configuration of strand or fiber material is specified
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/608Including strand or fiber material which is of specific structural definition
    • Y10T442/609Cross-sectional configuration of strand or fiber material is specified
    • Y10T442/611Cross-sectional configuration of strand or fiber material is other than circular
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/608Including strand or fiber material which is of specific structural definition
    • Y10T442/614Strand or fiber material specified as having microdimensions [i.e., microfiber]
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    • Y10T442/608Including strand or fiber material which is of specific structural definition
    • Y10T442/614Strand or fiber material specified as having microdimensions [i.e., microfiber]
    • Y10T442/619Including other strand or fiber material in the same layer not specified as having microdimensions
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    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
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    • Y10T442/614Strand or fiber material specified as having microdimensions [i.e., microfiber]
    • Y10T442/626Microfiber is synthetic polymer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/637Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T442/638Side-by-side multicomponent strand or fiber material
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    • Y10T442/637Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
    • Y10T442/64Islands-in-sea multicomponent strand or fiber material
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    • Y10T442/637Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
    • Y10T442/641Sheath-core multicomponent strand or fiber material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/696Including strand or fiber material which is stated to have specific attributes [e.g., heat or fire resistance, chemical or solvent resistance, high absorption for aqueous compositions, water solubility, heat shrinkability, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/697Containing at least two chemically different strand or fiber materials

Definitions

  • the present invention pertains to water-dispersible fibers and fibrous articles comprising a sulfopolyester.
  • the invention further pertains to multicomponent fibers comprising a sulfopolyester and the microdenier fibers and fibrous articles prepared therefrom.
  • the invention also pertains to processes for water-dispersible, multicomponent, and microdenier fibers and to nonwoven fabrics prepared therefrom.
  • the fibers and fibrous articles have applications in flushable personal care products and medical products.
  • Fibers, melt blown webs and other melt spun fibrous articles have been made from thermoplastic polymers, such as poly(propylene), polyamides, and polyesters.
  • thermoplastic polymers such as poly(propylene), polyamides, and polyesters.
  • One common application of these fibers and fibrous articles are nonwoven fabrics and, in particular, in personal care products such as wipes, feminine hygiene products, baby diapers, adult incontinence briefs, hospital/surgical and other medical disposables, protective fabrics and layers, geotextiles, industrial wipes, and filter media.
  • personal care products made from conventional thermoplastic polymers are difficult to dispose of and are usually placed in landfills.
  • One promising alternative method of disposal is to make these products or their components "flushable", i.e., compatible with public sewerage systems.
  • thermoplastic polymers now used in personal care products are not inherently water-dispersible or soluble and, hence, do not produce articles that readily disintegrate and can be disposed of in a sewerage system or recycled easily.
  • typical nonwoven technology is based on the multidirectional deposition of fibers that are treated with a resin binding adhesive to form a web having strong integrity and other desirable properties.
  • the resulting assemblies generally have poor water-responsivity and are not suitable for flushable applications.
  • the presence of binder also may result in undesirable properties in the final product, such as reduced sheet wettability, increased stiffness, stickiness, and higher production costs. It is also difficult to produce a binder that will exhibit adequate wet strength during use and yet disperse quickly upon disposal.
  • nonwoven assemblies using these binders may either disintegrate slowly under ambient conditions or have less than adequate wet strength properties in the presence of body fluids.
  • pH and ion-sensitive water-dispersible binders such as lattices containing acrylic or methacrylic acid with or without added salts, are known and described, for example, in U.S. Patent No. 6,548,592 Bl .
  • Ion concentrations and pH levels in public sewerage and residential septic systems can vary widely among geographical locations and may not be sufficient for the binder to become soluble and disperse. In this case, the fibrous articles will not disintegrate after disposal and can clog drains or sewer laterals.
  • Multicomponent fibers containing a water-dispersible component and a thermoplastic water non-dispersible component have been described, for example, in U.S. Patent No.'s 5,916,678; 5,405,698; 4,966,808; 5,525282; 5,366,804; 5,486,418.
  • these multicomponent fibers may be a bicomponent fiber having a shaped or engineered transverse cross section such as, for example, an islands-in-the- sea, sheath core, side-by-side, or segmented pie configuration.
  • the multicomponent fiber can be subjected to water or a dilute alkaline solution where the water- dispersible component is dissolved away to leave the water non-dispersible component behind as separate, independent fibers of extremely small fineness.
  • Polymers which have good water dispersibility often impart tackiness to the resulting multicomponent fibers, which causes the fiber to stick together, block, or fuse during winding or storage after several days, especially under hot, humid conditions.
  • a fatty acid or oil-based finish is applied to the surface of the fiber.
  • large proportions of pigments or fillers are sometimes added to water dispersible polymers to prevent fusing of the fibers as described, for example, in U.S. Patent No. 6,171,685.
  • Such oil finishes, pigments, and fillers require additional processing steps and can impart undesirable properties to the final fiber.
  • Many water-dispersible polymers also require alkaline solutions for their removal which can cause degradation of the other polymer components of the fiber such as, for example, reduction of inherent viscosity, tenacity, and melt strength. Further, some water-dispersible polymers can not withstand exposure to water during hydroentanglement and, thus, are not suitable for the manufacture of nonwoven webs and fabrics.
  • the water-dispersible component may serve as a bonding agent for the thermoplastic fibers in nonwoven webs. Upon exposure to water, the fiber to fiber bonds come apart such that the nonwoven web loses its integrity and breaks down into individual fibers.
  • the thermoplastic fiber components of these nonwoven webs are not water-dispersible and remain present in the aqueous medium and, thus, must eventually be removed from municipal wastewater treatment plants. Hydroentanglement may be used to produce disintegratable nonwoven fabrics without or with very low levels ( ⁇ 5 wt%) of added binder to hold the fibers together. Although these fabrics may disintegrate upon disposal, they often utilize fibers that are not water soluble or water-dispersible and may result in entanglement and plugging within sewer systems. Any added water-dispersible binders also must be minimally affected by hydroentangling and not form gelatinous buildup or cross-link, and thereby contribute to fabric handling or sewer related problems.
  • a few water-soluble or water-dispersible polymers are available, but are generally not applicable to melt blown fiber forming operations or melt spinning in general.
  • Polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylic acid are not melt processable as a result of thermal decomposition that occurs at temperatures below the point where a suitable melt viscosity is attained.
  • High molecular weight polyethylene oxide may have suitable thermal stability, but would provide a high viscosity solution at the polymer interface resulting in a slow rate of disintegration.
  • Water-dispersible sulfopolyesters have been described, for example, in U.S.
  • Typical sulfopolyesters are low molecular weight thermoplastics that are brittle and lack the flexibility to withstand a winding operation to yield a roll of material that does not fracture or crumble. Sulfopolyesters also can exhibit blocking or fusing during processing into film or fibers, which may require the use of oil finishes or large amounts of pigments or fillers to avoid. Low molecular weight polyethylene oxide (more commonly known as polyethylene glycol) is a weak/brittle polymer that also does not have the required physical properties for fiber applications. Forming fibers from known water-soluble polymers via solution techniques is an alternative, but the added complexity of removing solvent, especially water, increases manufacturing costs.
  • a water-dispersible fiber and fibrous articles prepared therefrom that exhibit adequate tensile strength, absorptivity, flexibility, and fabric integrity in the presence of moisture, especially upon exposure to human bodily fluids.
  • a fibrous article is needed that does not require a binder and completely disperses or dissolves in residential or municipal sewerage systems.
  • melt blown webs spunbond fabrics, hydroentangled fabrics, wet-laid nonwovens, dry-laid non-wovens, bicomponent fiber components, adhesive promoting layers, binders for cellulosics, flushable nonwovens and films, dissolvable binder fibers, protective layers, and carriers for active ingredients to be released or dissolved in water.
  • multicomponent fiber having a water-dispersible component that does not exhibit excessive blocking or fusing of filaments during spinning operations, is easily removed by hot water at neutral or slightly acidic pH, and is suitable for hydroentangling processes to manufacture nonwoven fabrics.
  • These multicomponent fibers can be utilized to produce microfibers that can be used to produce various articles. Other extrudable and melt spun fibrous materials are also possible.
  • a water- dispersible fiber comprising:
  • sulfopolyester having a glass transition temperature (Tg) of at least 25 0 C, the sulfopolyester comprising:
  • n is an integer in the range of 2 to about 500; and (iv) 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
  • (C) optionally, a water non-dispersible polymer blended with the sulfopolyester with the proviso that the blend is an immiscible blend; wherein the fiber contains less than 10 weight percent of a pigment or filler, based on the total weight of the fiber.
  • the fibers of the present invention may be unicomponent fibers that rapidly disperse or dissolve in water and may be produced by melt-blowing or melt-spinning.
  • the fibers may be prepared from a single sulfopolyester or a blend of the sulfopolyester with a water-dispersible or water non-dispersible polymer.
  • the fiber of the present invention optionally, may include a water-dispersible polymer blended with the sulfopolyester.
  • the fiber may optionally include a water non-dispersible polymer blended with the sulfopolyester, provided that the blend is an immiscible blend.
  • Our invention also includes fibrous articles comprising our water- dispersible fibers.
  • the fibers of our invention may be used to prepare various fibrous articles, such as yarns, melt-blown webs, spunbonded webs, and nonwoven fabrics that are, in turn, water-dispersible or flushable.
  • Staple fibers of our invention can also be blended with natural or synthetic fibers in paper, nonwoven webs, and textile yarns.
  • Another aspect of the present invention is a water-dispersible fiber comprising:
  • sulfopolyester having a glass transition temperature (Tg) of at least 25 0 C, the sulfopolyester comprising:
  • n is an integer in the range of 2 to about 500;
  • (C) optionally, a water non-dispersible polymer blended with the sulfopolyester to form a blend with the proviso that the blend is an immiscible blend; wherein the fiber contains less than 10 weight percent of a pigment or filler, based on the total weight of the fiber.
  • the water-dispersible, fibrous articles of the present invention include personal care articles such as, for example, wipes, gauze, tissue, diapers, training pants, sanitary napkins, bandages, wound care, and surgical dressings.
  • personal care articles such as, for example, wipes, gauze, tissue, diapers, training pants, sanitary napkins, bandages, wound care, and surgical dressings.
  • the fibrous articles of our invention are flushable, that is, compatible with and suitable for disposal in residential and municipal sewerage systems.
  • the present invention also provides a multicomponent fiber comprising a water-dispersible sulfopolyester and one or more water non-dispersible polymers.
  • the fiber has an engineered geometry such that the water non-dispersible polymers are present as segments substantially isolated from each other by the intervening sulfopolyester, which acts as a binder or encapsulating matrix for the water non- dispersible segments.
  • another aspect of our invention is a multicomponent fiber having a shaped cross section, comprising:
  • A a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 57 0 C, the sulfopolyester comprising: (i) residues of one or more dicarboxylic acids;
  • n is an integer in the range of 2 to about 500;
  • the sulfopolyester has a glass transition temperature of at least 57 0 C which greatly reduces blocking and fusion of the fiber during winding and long term storage.
  • the sulfopolyester may be removed by contacting the multicomponent fiber with water to leave behind the water non-dispersible segments as microdenier fibers.
  • Our invention therefore, also provides a process for microdenier fibers comprising: (A) spinning a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 57 0 C and one or more water non-dispersible polymers immiscible with the sulfopolyester into multicomponent fibers, the sulfopolyester comprising:
  • n is an integer in the range of 2 to about 500;
  • the water non-dispersible polymers may be biodistintegratable as determined by DIN Standard 54900 and/or biodegradable as determined by ASTM Standard Method, D6340-98.
  • the multicomponent fiber also may be used to prepare a fibrous article such as a yarn, fabric, melt-blown web, spun-bonded web, or non-woven fabric and which may comprise one or more layers of fibers.
  • the fibrous article having multicomponent fibers may be contacted with water to produce fibrous articles containing microdenier fibers.
  • Another aspect of the invention is a process for a microdenier fiber web, comprising:
  • A spinning a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 57 0 C and one or more water non-dispersible polymers immiscible with the sulfopolyester into multicomponent fibers, the sulfopolyester comprising:
  • n is an integer in the range of 2 to about 500;
  • the multicomponent fibers have a plurality of segments comprising the water non-dispersible polymers and the segments are substantially isolated from each other by the sulfopolyester intervening between the segments and the fibers contain less than 10 weight percent of a pigment or filler, based on the total weight of said fibers;
  • Our invention also provides a process making a water-dispersible, nonwoven fabric comprising:
  • n is an integer in the range of 2 to about 500; (d) 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
  • a multicomponent fiber having a shaped cross section, comprising:
  • a multicomponent extrudate having a shaped cross section comprising:
  • a process for making a multicomponent fiber having a shaped cross section comprising spinning at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with the sulfopolyester, wherein the multicomponent fiber has a plurality of domains comprising the water non-dispersible polymers and the domains are substantially isolated from each other by the sulfopolyester intervening between the domains; wherein the multicomponent fiber has an as-spun denier of less than about 6 denier per filament; wherein the water dispersible sulfopolyester exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprises less than about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residue
  • a process for making a multicomponent fiber having a shaped cross section comprising extruding at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with the sulfopolyester to produce a multicomponent extrudate, wherein the multicomponent extrudate has a plurality of domains comprising said water non-dispersible polymers and said domains are substantially isolated from each other by said sulfopolyester intervening between said domains; and melt drawing the multicomponent extrudate at a speed of at least about 2000 m/min to produce the multicomponent fiber.
  • the present invention provides a process for producing microdenier fibers comprising:
  • the present invention provides a process for producing microdenier fibers comprising:
  • a process for making a microdenier fiber web comprising:
  • the multicomponent fibers have a plurality of domains comprising the water non-dispersible polymers wherein the domains are substantially isolated from each other by the water dispersible sulfopolyester intervening between the domains; wherein the multicomponent fiber has an as-spun denier of less than about 6 denier per filament; wherein the water dispersible sulfopolyester exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprising less than, about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residues;
  • Step (B) collecting the multicomponent fibers of Step (A) to form a non-woven web
  • a process for making a microdenier fiber web comprising:
  • Step (C) collecting the multicomponent fibers of Step (B) to form a non-woven web
  • a process for producing a water non- dispersible polymer microfiber comprising: a) cutting a multicomponent fiber into cut multicomponent fibers; b) contacting a fiber-containing feedstock with water to produce a fiber mix slurry; wherein the fiber-containing feedstock comprises cut multicomponent fibers; c) heating the fiber mix slurry to produce a heated fiber mix slurry; d) optionally, mixing the fiber mix slurry in a shearing zone; e) removing at least a portion of the sulfopolyester from the multicomponent fiber to produce a slurry mixture comprising a sulfopolyester dispersion and the water non-dispersible polymer microfibers; and f) separating the water non-dispersible polymer microfibers from the slurry mixture.
  • the water non-dispersible polymer microf ⁇ ber comprising at least one water non-dispersible polymer wherein the water non-dispersible polymer microfiber has an equivalent diameter of less than 5 microns and length of less than 25 millimeters.
  • a process for producing a nonwoven article from the water non-dispersible polymer microfiber comprising: a) providing a water non-dispersible polymer microfiber produced from a multicomponent fiber; and b) producing the nonwoven article utilizing a wet-laid process or a dry-laid process.
  • the present invention provides water-dispersible fibers and fibrous articles that show tensile strength, absorptivity, flexibility, and fabric integrity in the presence of moisture, especially upon exposure to human bodily fluids.
  • the fibers and fibrous articles of our invention do not require the presence of oil, wax, or fatty acid finishes or the use of large amounts (typically 10 wt% or greater) of pigments or fillers to prevent blocking or fusing of the fibers during processing.
  • the fibrous articles prepared from our novel fibers do not require a binder and readily disperse or dissolve in home or public sewerage systems.
  • our invention provides a water-dispersible fiber comprising a sulfopolyester having a glass transition temperature (Tg) of at least 25 0 C, wherein the sulfopolyester comprises: (A) residues of one or more dicarboxylic acids; (B) about 4 to about 40 mole%, based on the total repeating units, of residues of at least one sulfomonomer having 2 functional groups and one or more sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
  • our fiber may optionally include a water-dispersible polymer blended with the sulfopolyester and, optionally, a water non-dispersible polymer blended with the sulfopolyester with the proviso that the blend is an immiscible blend.
  • Our fiber contains less than 10 weight percent of a pigment or filler, based on the total weight of the fiber.
  • the present invention also includes fibrous articles comprising these fibers and may include personal care products such as wipes, gauze, tissue, diapers, adult incontinence briefs, training pants, sanitary napkins, bandages, and surgical dressings.
  • the fibrous articles may have one or more absorbent layers of fibers.
  • the fibers of our invention may be unicomponent fibers, bicomponent or multicomponent fibers.
  • the fibers of the present invention may be prepared by melt spinning a single sulfopolyester or sulfopolyester blend and include staple, monofilament, and multifilament fibers with a shaped cross-section.
  • our invention provides multicomponent fibers, such as described, for example, in U.S. Patent No.
  • 5,916,678 which may be prepared by extruding the sulfopolyester and one or more water non-dispersible polymers, which are immiscible with the sulfopolyester, separately through a spinneret having a shaped or engineered transverse geometry such as, for example, an "islands-in-the-sea", sheath-core, side- by-side, or segmented pie configuration.
  • the sulfopolyester may be later removed by dissolving the interfacial layers or pie segments and leaving the smaller filaments or microdenier fibers of the water non-dispersible polymer(s).
  • These fibers of the water non-dispersible polymer have fiber size much smaller than the multi-component fiber before removing the sulfopolyester.
  • the sulfopolyester and water non- dispersible polymers may be fed to a polymer distribution system where the polymers are introduced into a segmented spinneret plate.
  • the polymers follow separate paths to the fiber spinneret and are combined at the spinneret hole which comprises either two concentric circular holes thus providing a sheath-core type fiber, or a circular spinneret hole divided along a diameter into multiple parts to provide a fiber having a side-by-side type.
  • the immiscible water dispersible sulfopolyester and water non-dispersible polymers may be introduced separately into a spinneret having a plurality of radial channels to produce a multicomponent fiber having a segmented pie cross section.
  • the sulfopolyester will form the "sheath" component of a sheath core configuration.
  • the water non-dispersible segments typically, are substantially isolated from each other by the sulfopolyester.
  • multicomponent fibers may be formed by melting the sulfopolyester and water non-dispersible polymers in separate extruders and directing the polymer flows into one spinneret with a plurality of distribution flow paths in form of small thin tubes or segments to provide a fiber having an islands-in- the-sea shaped cross section.
  • a spinneret is described in U.S. Patent No. 5,366,804.
  • the sulfopolyester will form the "sea” component and the water non-dispersible polymer will form the "islands" component.
  • a range stated to be 0 to 10 is intended to disclose all whole numbers between 0 and 10 such as, for example 1, 2, 3, 4, etc., all fractional numbers between 0 and 10, for example 1.5, 2.3, 4.57, 6.1113, etc., and the endpoints 0 and 10.
  • a range associated with chemical substituent groups such as, for example, "Cl to C5 hydrocarbons”, is intended to specifically include and disclose Cl and C5 hydrocarbons as well as C2, C3, and C4 hydrocarbons.
  • the unicomponent fibers and fibrous articles produced from the unicomponent fibers of the present invention are water-dispersible and, typically, completely disperse at room temperature. Higher water temperatures can be used to accelerate their dispersibility or rate of removal from the nonwoven or multicomponent fiber.
  • water-dispersible as used herein with respect to unicomponent fibers and fibrous articles prepared from unicomponent fibers, is intended to be synonymous with the terms “water-dissipatable”, “water-disintegratable”, “water-dissolvable”, “water-dispellable”, “water soluble”, water-removable”, “hydrosoluble”, and “hydrodispersible” and is intended to mean that the fiber or fibrous article is therein or therethrough dispersed or dissolved by the action of water.
  • dissipate means that, using a sufficient amount of deionized water (e.g., 100:1 water.fiber by weight) to form a loose suspension or slurry of the fibers or fibrous article, at a temperature of about 6O 0 C, and within a time period of up to 5 days, the fiber or fibrous article dissolves, disintegrates, or separates into a plurality of incoherent pieces or particles distributed more or less throughout the medium such that no recognizable filaments are recoverable from the medium upon removal of the water, for example, by filtration or evaporation.
  • deionized water e.g. 100:1 water.fiber by weight
  • water- dispersible is not intended to include the simple disintegration of an assembly of entangled or bound, but otherwise water insoluble or nondispersible, fibers wherein the fiber assembly simply breaks apart in water to produce a slurry of fibers in water which could be recovered by removal of the water.
  • all of these terms refer to the activity of water or a mixture of water and a water-miscible cosolvent on the sulfopolyesters described herein. Examples of such water-miscible cosolvents includes alcohols, ketones, glycol ethers, esters and the like.
  • water-dispersible as used herein in reference to the sulfopolyester as one component of a multicomponent fiber or fibrous article, also is intended to be synonymous with the terms “water-dissipatable”, “water- disintegratable”, “water-dissolvable”, “water-dispellable”, “water soluble”, “water- removable”, “hydrosoluble”, and “hydrodispersible” and is intended to mean that the sulfopolyester component is sufficiently removed from the multicomponent fiber and is dispersed or dissolved by the action of water to enable the release and separation of the water non-dispersible fibers contained therein.
  • dissipate means that, using a sufficient amount of deionized water (e.g., 100:1 wate ⁇ fiber by weight) to form a loose suspension or slurry of the fibers or fibrous article, at a temperature of about 6O 0 C, and within a time period of up to 5 days, sulfopolyester component dissolves, disintegrates, or separates from the multicomponent fiber, leaving behind a plurality of microdenier fibers from the water non-dispersible segments.
  • deionized water e.g., 100:1 wate ⁇ fiber by weight
  • segment or “domain” or “zone” when used to describe the shaped cross section of a multicomponent fiber refers to the area within the cross section comprising the water non-dispersible polymers where these domains or segments are substantially isolated from each other by the water-dispersible sulfopolyester intervening between the segments or domains.
  • substantially isolated as used herein, is intended to mean that the segments or domains are set apart from each other to permit the segments domains to form individual fibers upon removal of the sulfopolyester.
  • Segments or domains or zones can be of similar size and shape or varying size and shape. Again, segments or domains or zones can be arranged in any configuration.
  • segments or domains or zones are “substantially continuous” along the length of the multicomponent extrudate or fiber.
  • the term “substantially continuous” means continuous along at least 10 cm length of the multicomponent fiber.
  • the shaped cross section of a multicomponent fiber can, for example, be in the form of a sheath core, islands-in-the sea, segmented pie, hollow segmented pie; off-centered segmented pie, etc..
  • the water-dispersible fiber of the present invention is prepared from polyesters or, more specifically sulfopolyesters, comprising dicarboxylic acid monomer residues, sulfomonomer residues, diol monomer residues, and repeating units.
  • the sulfomonomer may be a dicarboxylic acid, a diol, or hydroxycarboxylic acid.
  • the term "monomer residue”, as used herein, means a residue of a dicarboxylic acid, a diol, or a hydroxycarboxylic acid.
  • a “repeating unit”, as used herein, means an organic structure having 2 monomer residues bonded through a carbonyloxy group.
  • the sulfopolyesters of the present invention contain substantially equal molar proportions of acid residues (100 mole %) and diol residues (100 mole %) which react in substantially equal proportions such that the total moles of repeating units is equal to 100 mole %.
  • the mole percentages provided in the present disclosure therefore, may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units.
  • a sulfopolyester containing 30 mole% of a sulfomonomer, which may be a dicarboxylic acid, a diol, or hydroxycarboxylic acid, based on the total repeating units means that the sulfopolyester contains 30 mole% sulfomonomer out of a total of 100 mole% repeating units. Thus, there are 30 moles of sulfomonomer residues among every 100 moles of repeating units.
  • a sulfopolyester containing 30 mole% of a dicarboxylic acid sulfomonomer, based on the total acid residues means the sulfopolyester contains 30 mole% sulfomonomer out of a total of 100 mole% acid residues.
  • the sulfopolyesters described herein have an inherent viscosity, abbreviated hereinafter as "Ih.V.”, of at least about 0.1 dL/g, preferably about 0.2 to 0.3 dL/g, and most preferably greater than about 0.3 dL/g, measured in a 60/40 parts by weight solution of phenol/tetrachloroethane solvent at 25 0 C and at a concentration of about 0.5 g of sulfopolyester in 100 mL of solvent.
  • Ih.V inherent viscosity
  • polystyrene resin encompasses both “homopolyesters” and “copolyesters” and means a synthetic polymer prepared by the polycondensation of difunctional carboxylic acids with difunctional hydroxyl compound.
  • sulfopolyester means any polyester comprising a sulfomonomer.
  • the difunctional carboxylic acid is a dicarboxylic acid and the difunctional hydroxyl compound is a dihydric alcohol such as, for example glycols and diols.
  • the difunctional carboxylic acid may be a hydroxy carboxylic acid such as, for example, p-hydroxybenzoic acid
  • the difunctional hydroxyl compound may be a aromatic nucleus bearing 2 hydroxy substituents such as, for example, hydroquinone.
  • the term "residue”, as used herein, means any organic structure incorporated into the polymer through a polycondensation reaction involving the corresponding monomer.
  • the dicarboxylic acid residue may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof.
  • dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half- esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process with a diol to make a high molecular weight polyester.
  • the sulfopolyester of the present invention includes one or more dicarboxylic acid residues.
  • the dicarboxylic acid residue may comprise from about 60 to about 100 mole% of the acid residues.
  • concentration ranges of dicarboxylic acid residues are from about 60 mole% to about 95 mole%, and about 70 mole% to about 95 mole%.
  • dicarboxylic acids that may be used include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, or mixtures of two or more of these acids.
  • suitable dicarboxylic acids include, but are not limited to, succinic; glutaric; adipic; azelaic; sebacic; fumaric; maleic; itaconic; 1,3-cyclohexanedicarboxylic; 1,4-cyclohexanedicarboxylic; diglycolic; 2,5- norbornanedicarboxylic; phthalic; terephthalic; 1,4-naphthalenedicarboxylic; 2,5- naphthalenedicarboxylic; diphenic; 4,4'-oxydibenzoic; 4,4'-sulfonyidibenzoic; and isophthalic.
  • the preferred dicarboxylic acid residues are isophthalic, terephthalic, and 1,4-cyclohexanedicarboxylic acids, or if diesters are used, dimethyl terephthalate, dimethyl isophthalate, and dimethyl-l,4-cyclohexanedicarboxylate with the residues of isophthalic and terephthalic acid being especially preferred.
  • dicarboxylic acid methyl ester is the most preferred embodiment, it is also acceptable to include higher order alkyl esters, such as ethyl, propyl, isopropyl, butyl, and so forth.
  • aromatic esters, particularly phenyl also may be employed.
  • the sulfopolyester includes about 4 to about 40 mole%, based on the total repeating units, of residues of at least one sulfomonomer having 2 functional groups and one or more sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof. Additional examples of concentration ranges for the sulfomonomer residues are about 4 to about 35 mole%, about 8 to about 30 mole%, and about 8 to about 25 mole%, based on the total repeating units.
  • the sulfomonomer may be a dicarboxylic acid or ester thereof containing a sulfonate group, a diol containing a sulfonate group, or a hydroxy acid containing a sulfonate group.
  • sulfonate refers to a salt of a sulfonic acid having the structure "-SO 3 M" wherein M is the cation of the sulfonate salt.
  • the cation of the sulfonate salt may be a metal ion such as Li + , Na + , K + , Mg + ⁇ Ca ⁇ + , Ni +"1" , Fe +"1” , and the like.
  • the cation of the sulfonate salt may be non-metallic such as a nitrogenous base as described, for example, in U.S. Patent No. 4,304,901.
  • Nitrogen- based cations are derived from nitrogen-containing bases, which may be aliphatic, cycloaliphatic, or aromatic compounds. Examples of such nitrogen containing bases include ammonia, dimethylethanolamine, diethanolamine, triethanolamine, pyridine, morpholine, and piperidine.
  • the method of this invention for preparing sulfopolyesters containing nitrogen-based sulfonate salt groups is to disperse, dissipate, or dissolve the polymer containing the required amount of sulfonate group in the form of its alkali metal salt in water and then exchange the alkali metal cation for a nitrogen-based cation.
  • the resulting sulfopolyester is completely dispersible in water with the rate of dispersion dependent on the content of sulfomonomer in the polymer, temperature of the water, surface area/thickness of the sulfopolyester, and so forth.
  • a divalent metal ion is used, the resulting sulfopolyesters are not readily dispersed by cold water but are more easily dispersed by hot water. Utilization of more than one counterion within a single polymer composition is possible and may offer a means to tailor or fine-tune the water-responsivity of the resulting article of manufacture.
  • sulfomonomers residues include monomer residues where the sulfonate salt group is attached to an aromatic acid nucleus, such as, for example, benzene; naphthalene; diphenyl; oxydiphenyl; sulfonyldiphenyl; and methylenediphenyl or cycloaliphatic rings, such as, for example, cyclohexyl; cyclopentyl; cyclobutyl; cycloheptyl; and cyclooctyl.
  • aromatic acid nucleus such as, for example, benzene; naphthalene; diphenyl; oxydiphenyl; sulfonyldiphenyl; and methylenediphenyl or cycloaliphatic rings, such as, for example, cyclohexyl; cyclopentyl; cyclobutyl; cycloheptyl; and cyclooctyl.
  • sulfomonomer residues which may be used in the present invention are the metal sulfonate salt of sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalic acid, or combinations thereof.
  • sulfomonomers which may be used are 5-sodiosulfoisophthalic acid and esters thereof. If the sulfomonomer residue is from 5-sodiosulfoisophthalic acid, typical sulfomonomer concentration ranges are about 4 to about 35 mole%, about 8 to about 30 mole %, and about 8 to 25 mole %, based on the total moles of acid residues.
  • the sulfomonomers used in the preparation of the sulfopoly esters are known compounds and may be prepared using methods well known in the art.
  • sulfomonomers in which the sulfonate group is attached to an aromatic ring may be prepared by sulfonating the aromatic compound with oleum to obtain the corresponding sulfonic acid and followed by reaction with a metal oxide or base, for example, sodium acetate, to prepare the sulfonate salt.
  • Procedures for preparation of various sulfomonomers are described, for example, in U.S. Patent No.'s 3,779,993; 3,018,272; and 3,528,947.
  • polyester using, for example, a sodium sulfonate salt, and ion-exchange methods to replace the sodium with a different ion, such as zinc, when the polymer is in the dispersed form.
  • a sodium sulfonate salt and ion-exchange methods to replace the sodium with a different ion, such as zinc, when the polymer is in the dispersed form.
  • This type of ion exchange procedure is generally superior to preparing the polymer with divalent salts insofar as the sodium salts are usually more soluble in the polymer reactant melt-phase.
  • the sulfopolyester includes one or more diol residues which may include aliphatic, cycloaliphatic, and aralkyl glycols.
  • the cycloaliphatic diols for example, 1,3- and 1 ,4-cyclohexanedimethanol, may be present as their pure cis or trans isomers or as a mixture of cis and trans isomers.
  • diol is synonymous with the term "glycol” and means any dihydric alcohol.
  • diols include, but are not limited to, ethylene glycol; diethylene glycol; triethylene glycol; polyethylene glycols; 1 ,3-propanediol; 2,4-dimethyl-2-ethylhexane-l,3-diol; 2,2-dimethyl- 1 ,3-propanediol; 2-ethyl-2-butyl- 1 ,3-propanediol; 2-ethyl-2-isobutyl- 1,3-propanediol; 1 ,3-butanediol; 1,4-butanediol; 1,5-pentanediol; 1 ,6-hexanediol; 2,2,4-trimethyl-l,6-hexanediol; thiodiethanol; 1 ,2-cyclohexanedimethanol; 1,3- cyclohexanedimethanol; 1 ,4-cyclohexan
  • the diol residues may include from about 25 mole% to about 100 mole%, based on the total diol residues, of residue of a poly(ethylene glycol) having a structure
  • n is an integer in the range of 2 to about 500.
  • lower molecular weight polyethylene glycols e.g., wherein n is from 2 to 6, are diethylene glycol, triethylene glycol, and tetraethylene glycol. Of these lower molecular weight glycols, diethylene and triethylene glycol are most preferred.
  • Higher molecular weight polyethylene glycols (abbreviated herein as "PEG"), wherein n is from 7 to about 500, include the commercially available products known under the designation C ARBO WAX®, a product of Dow Chemical Company (formerly Union Carbide).
  • PEGs are used in combination with other diols such as, for example, diethylene glycol or ethylene glycol.
  • diols such as, for example, diethylene glycol or ethylene glycol.
  • the molecular weight may range from greater than 300 to about 22,000 g/mol.
  • the molecular weight and the mole% are inversely proportional to each other; specifically, as the molecular weight is increased, the mole % will be decreased in order to achieve a designated degree of hydrophilicity.
  • a PEG having a molecular weight of 1000 may constitute up to 10 mole% of the total diol, while a PEG having a molecular weight of 10,000 would typically be incorporated at a level of less than 1 mole% of the total diol.
  • dimer, trimer, and tetramer diols may be formed in situ due to side reactions that may be controlled by varying the process conditions.
  • varying amounts of diethylene, triethylene, and tetraethylene glycols may be formed from ethylene glycol from an acid-catalyzed dehydration reaction which occurs readily when the polycondensation reaction is carried out under acidic conditions.
  • the presence of buffer solutions may be added to the reaction mixture to retard these side reactions. Additional compositional latitude is possible, however, if the buffer is omitted and the dimerization, trimerization, and tetramerization reactions are allowed to proceed.
  • the sulfopolyester of the present invention may include from 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof.
  • branching monomers are 1,1,1- trimethylol propane, 1,1 ,1-trimethylolethane, glycerin, pentaerythritol, erythritol, threitol, dipentaerythritol, sorbitol, trimellitic anhydride, pyromellitic dianhydride, dimethylol propionic acid, or combinations thereof.
  • branching monomer concentration ranges are from 0 to about 20 mole% and from 0 to about 10 mole%.
  • the presence of a branching monomer may result in a number of possible benefits to the sulfopolyester of the present invention, including but not limited to, the ability to tailor rheological, solubility, and tensile properties.
  • a branched sulfopolyester compared to a linear analog, will also have a greater concentration of end groups that may facilitate post- polymerization crosslinking reactions.
  • branching agent At high concentrations of branching agent, however, the sulfopolyester may be prone to gelation.
  • the sulfopolyester used for the fiber of the present invention has a glass transition temperature, abbreviated herein as "Tg", of at least 25 0 C as measured on the dry polymer using standard techniques, such as differential scanning calorimetry ("DSC"), well known to persons skilled in the art.
  • Tg measurements of the sulfopolyesters of the present invention are conducted using a "dry polymer", that is, a polymer sample in which adventitious or absorbed water is driven off by heating to polymer to a temperature of about 200 0 C and allowing the sample to return to room temperature.
  • the sulfopolyester is dried in the DSC apparatus by conducting a first thermal scan in which the sample is heated to a temperature above the water vaporization temperature, holding the sample at that temperature until the vaporization of the water absorbed in the polymer is complete (as indicated by an a large, broad endotherm), cooling the sample to room temperature, and then conducting a second thermal scan to obtain the Tg measurement.
  • Further examples of glass transition temperatures exhibited by the sulfopolyester are at least 3O 0 C, at least 35 0 C, at least 4O 0 C, at least 5O 0 C, at least 6O 0 C, at least 65 0 C, at least 8O 0 C, and at least 9O 0 C.
  • typical glass transition temperatures of the dry sulfopolyesters our invention are about 3O 0 C, about 48 0 C, about 55 0 C, about 65°C, about 7O 0 C, about 75 0 C, about 85 0 C, and about 9O 0 C.
  • our novel fibers may consist essentially of or, consist of, the sulfopolyesters described hereinabove.
  • the sulfopolyesters of this invention may be a single polyester or may be blended with one or more supplemental polymers to modify the properties of the resulting fiber.
  • the supplemental polymer may or may not be water-dispersible depending on the application and may be miscible or immiscible with the sulfopolyester. If the supplemental polymer is water non-dispersible, it is preferred that the blend with the sulfopolyester is immiscible.
  • miscible is intended to mean that the blend has a single, homogeneous amorphous phase as indicated by a single composition-dependent Tg.
  • a first polymer that is miscible with second polymer may be used to "plasticize” the second polymer as illustrated, for example, in U.S. Patent No. 6,21 1,309.
  • the term “immiscible”, as used herein denotes a blend that shows at least 2, randomly mixed, phases and exhibits more than one Tg. Some polymers may be immiscible and yet compatible with the sulfopolyester.
  • Non-limiting examples of water-dispersible polymers that may be blended with the sulfopolyester are polymethacrylic acid, polyvinyl pyrrolidone, polyethylene- acrylic acid copolymers, polyvinyl methyl ether, polyvinyl alcohol, polyethylene oxide, hydroxy propyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, isopropyl cellulose, methyl ether starch, polyacrylamides, poly(N-vinyl caprolactam), polyethyl oxazoline, poly(2-isopropyl-2- oxazoline), polyvinyl methyl oxazolidone, water-dispersible sulfopolyesters, polyvinyl methyl oxazolidimone, poly(2,4-dimethyl-6-triazinylethylene), and ethylene oxide-propylene oxide copolymers.
  • polyolefins such as homo- and copolymers of polyethylene and polypropylene
  • poly(ethylene terephthalate) poly(butylene terephthalate)
  • polyamides such as nylon-6
  • polylactides such as caprolactone
  • Eastar Bio ® poly(tetramethylene adipate-co- terephthalate), a product of Eastman Chemical Company
  • blends of more than one sulfopolyester may be used to tailor the end-use properties of the resulting fiber or fibrous article, for example, a nonwoven fabric or web.
  • the blends of one or more sulfopolyesters will have Tg' s of at least 25 0 C for the water-dispersible, unicomponent fibers and at least 57 0 C for the multicomponent fibers.
  • Tg' s of at least 25 0 C for the water-dispersible, unicomponent fibers and at least 57 0 C for the multicomponent fibers.
  • blending may also be exploited to alter the processing characteristics of a sulfopolyester to facilitate the fabrication of a nonwoven.
  • an immiscible blend of polypropylene and sulfopolyester may provide a conventional nonwoven web that will break apart and completely disperse in water as true solubility is not needed.
  • the desired performance is related to maintaining the physical properties of the polypropylene while the sulfopolyester is only a spectator during the actual use of the product or, alternatively, the sulfopolyester is fugitive and is removed before the final form of the product is utilized.
  • the sulfopolyester and supplemental polymer may be blended in batch, semicontinuous, or continuous processes. Small scale batches may be readily prepared in any high-intensity mixing devices well-known to those skilled in the art, such as Banbury mixers, prior to melt-spinning fibers. The components may also be blended in solution in an appropriate solvent.
  • the melt blending method includes blending the sulfopolyester and supplemental polymer at a temperature sufficient to melt the polymers. The blend may be cooled and pelletized for further use or the melt blend can be melt spun directly from this molten blend into fiber form.
  • the term "melt" as used herein includes, but is not limited to, merely softening the polyester. For melt mixing methods generally known in the polymers art, see Mixing and Compounding of Polymers (I. Manas-Zloczower & Z. Tadmor editors, Carl Hanser Verlag Publisher, 1994, New York, N. Y.).
  • Our invention also provides a water-dispersible fiber comprising a sulfopolyester having a glass transition temperature (Tg) of at least 25 0 C, wherein the sulfopolyester comprises: (A) about 50 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid, based on the total acid residues;
  • the fiber may optionally include a first water-dispersible polymer blended with the sulfopolyester; and, optionally, a water non-dispersible polymer blended with the sulfopolyester such that the blend is an immiscible blend.
  • Our fiber contains less than 10 weight percent of a pigment or filler, based on the total weight of the fiber.
  • the first water-dispersible polymer is as described hereinabove.
  • the sulfopolyester should have a glass transition temperature (Tg) of at least 25 0 C, but may have, for example, a Tg of about 35 0 C, about 48 0 C, about 55 0 C, about 65 0 C, about 7O 0 C, about 75 0 C, about 85 0 C, and about 9O 0 C.
  • Tg glass transition temperature
  • the sulfopolyester may contain other concentrations of isophthalic acid residues, for example, about 60 to about 95 mole%, and about 75 to about 95 mole%.
  • isophthalic acid residue concentrations ranges are about 70 to about 85 mole%, about 85 to about 95 mole% and about 90 to about 95 mole%.
  • the sulfopolyester also may comprise about 25 to about 95 mole% of the residues of diethylene glycol. Further examples of diethylene glycol residue concentration ranges include about 50 to about 95 mole%, about 70 to about 95 mole%, and about 75 to about 95 mole%.
  • the sulfopolyester also may include the residues of ethylene glycol and/or 1,4-cyclohexanedimethanol, abbreviated herein as "CHDM".
  • Typical concentration ranges of CHDM residues are about 10 to about 75 mole%, about 25 to about 65 mole%, and about 40 to about 60 mole%.
  • Typical concentration ranges of ethylene glycol residues are about 10 to about 75 mole%, about 25 to about 65 mole%, and about 40 to about 60 mole%.
  • the sulfopolyester comprises is about 75 to about 96 mole% of the residues of isophthalic acid and about 25 to about 95 mole% of the residues of diethylene glycol.
  • the sulfopolyesters of the instant invention are readily prepared from the appropriate dicarboxylic acids, esters, anhydrides, or salts, sulfomonomer, and the appropriate diol or diol mixtures using typical polycondensation reaction conditions. They may be made by continuous, semi-continuous, and batch modes of operation and may utilize a variety of reactor types. Examples of suitable reactor types include, but are not limited to, stirred tank, continuous stirred tank, slurry, tubular, wiped-film, falling film, or extrusion reactors.
  • continuous as used herein means a process wherein reactants are introduced and products withdrawn simultaneously in an uninterrupted manner.
  • continuous it is meant that the process is substantially or completely continuous in operation and is to be contrasted with a “batch” process.
  • Continuous is not meant in any way to prohibit normal interruptions in the continuity of the process due to, for example, start-up, reactor maintenance, or scheduled shut down periods.
  • batch process as used herein means a process wherein all the reactants are added to the reactor and then processed according to a predetermined course of reaction during which no material is fed or removed into the reactor.
  • continuous means a process where some of the reactants are charged at the beginning of the process and the remaining reactants are fed continuously as the reaction progresses.
  • a semicontinuous process may also include a process similar to a batch process in which all the reactants are added at the beginning of the process except that one or more of the products are removed continuously as the reaction progresses.
  • the process is operated advantageously as a continuous process for economic reasons and to produce superior coloration of the polymer as the sulfopolyester may deteriorate in appearance if allowed to reside in a reactor at an elevated temperature for too long a duration.
  • the sulfopolyesters of the present invention are prepared by procedures known to persons skilled in the art.
  • the sulfomonomer is most often added directly to the reaction mixture from which the polymer is made, although other processes are known and may also be employed, for example, as described in U. S. Patent No.'s 3,018,272, 3,075,952, and 3,033,822.
  • the reaction of the sulfomonomer, diol component and the dicarboxylic acid component may be carried out using conventional polyester polymerization conditions.
  • the reaction process may comprise two steps.
  • the diol component and the dicarboxylic acid component are reacted at elevated temperatures, typically, about 15O 0 C to about 25O 0 C for about 0.5 to about 8 hours at pressures ranging from about 0.0 kPa gauge to about 414 kPa gauge (60 pounds per square inch, "psig").
  • the temperature for the ester interchange reaction ranges from about 18O 0 C to about 23O 0 C for about 1 to about 4 hours while the preferred pressure ranges from about 103 kPa gauge (15 psig) to about 276 kPa gauge (40 psig).
  • reaction product is heated under higher temperatures and under reduced pressure to form sulfopolyester with the elimination of diol, which is readily volatilized under these conditions and removed from the system.
  • This second step, or polycondensation step is continued under higher vacuum and a temperature which generally ranges from about 23O 0 C. to about 35O 0 C, preferably about 25O 0 C to about 31O 0 C and most preferably about 26O 0 C to about 29O 0 C for about 0.1 to about 6 hours, or preferably, for about 0.2 to about 2 hours, until a polymer having the desired degree of polymerization, as determined by inherent viscosity, is obtained.
  • the polycondensation step may be conducted under reduced pressure which ranges from about 53 kPa (400 torr) to about 0.013 kPa (0.1 torr). Stirring or appropriate conditions are used in both stages to ensure adequate heat transfer and surface renewal of the reaction mixture.
  • the reactions of both stages are facilitated by appropriate catalysts such as, for example, alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyl tin compounds, metal oxides, and the like.
  • a three-stage manufacturing procedure similar to that described in U.S. Patent No. 5,290,631 , may also be used, particularly when a mixed monomer feed of acids and esters is employed.
  • sulfopolyesters are produced by reacting the dicarboxylic acid or a mixture of dicarboxylic acids with the diol component or a mixture of diol components.
  • the reaction is conducted at a pressure of from about 7 kPa gauge (1 psig) to about 1379 kPa gauge (200 psig), preferably less than 689 kPa (100 psig) to produce a low molecular weight, linear or branched sulfopolyester product having an average degree of polymerization of from about 1.4 to about 10.
  • the temperatures employed during the direct esterification reaction typically range from about 18O 0 C to about 28O 0 C, more preferably ranging from about 22O 0 C to about 27O 0 C.
  • This low molecular weight polymer may then be polymerized by a polycondensation reaction.
  • the water dispersible and multicomponent fibers and fibrous articles of this invention also may contain other conventional additives and ingredients which do not deleteriously affect their end use.
  • additives such as fillers, surface friction modifiers, light and heat stabilizers, extrusion aids, antistatic agents, colorants, dyes, pigments, fluorescent brighteners, antimicrobials, anticounterfeiting markers, hydrophobic and hydrophilic enhancers, viscosity modifiers, slip agents, tougheners, adhesion promoters, and the like may be used.
  • the fibers and fibrous articles of our invention do not require the presence of additives such as, for example, pigments, fillers, oils, waxes, or fatty acid finishes, to prevent blocking or fusing of the fibers during processing.
  • additives such as, for example, pigments, fillers, oils, waxes, or fatty acid finishes
  • blocking or fusing is understood to mean that the fibers or fibrous articles stick together or fuse into a mass such that the fiber cannot be processed or used for its intended purpose. Blocking and fusing can occur during processing of the fiber or fibrous article or during storage over a period of days or weeks and is exacerbated under hot, humid conditions.
  • the fibers and fibrous articles will contain less than 10 wt% of such anti-blocking additives, based on the total weight of the fiber or fibrous article.
  • the fibers and fibrous articles may contain less than 10 wt% of a pigment or filler.
  • the fibers and fibrous articles may contain less than 9 wt%, less than 5 wt%, less than 3 wt%, less than 1 wt%, and 0 wt% of a pigment or filler, based on the total weight of the fiber.
  • Colorants sometimes referred to as toners, may be added to impart a desired neutral hue and/or brightness to the sulfopolyester.
  • pigments or colorants may be included in the sulfopolyester reaction mixture during the reaction of the diol monomer and the dicarboxylic acid monomer or they may be melt blended with the preformed sulfopolyester.
  • a preferred method of including colorants is to use a colorant having thermally stable organic colored compounds having reactive groups such that the colorant is copolymerized and incorporated into the sulfopolyester to improve its hue.
  • colorants such as dyes possessing reactive hydroxyl and/or carboxyl groups, including, but not limited to, blue and red substituted anthraquinones, may be copolymerized into the polymer chain.
  • dyes When dyes are employed as colorants, they may be added to the copolyester reaction process after an ester interchange or direct esterification reaction.
  • the term “fiber” refers to a polymeric body of high aspect ratio capable of being formed into two or three dimensional articles such as woven or nonwoven fabrics.
  • the term “fiber” is synonymous with “fibers” and intended to mean one or more fibers.
  • the fibers of our invention may be unicomponent fibers, bicomponent, or multicomponent fibers.
  • the term "unicomponent fiber”, as used herein, is intended to mean a fiber prepared by melt spinning a single sulfopolyester, blends of one or more sulfopolyesters, or blends of one or more sulfopolyesters with one or more additional polymers and includes staple, monofilament, and multifilament fibers.
  • Unicomponent is intended to be synonymous with the term “monocomponent” and includes “biconstituent” or “multiconstituent” fibers, and refers to fibers which have been formed from at least two polymers extruded from the same extruder as a blend. Unicomponent or biconstituent fibers do not have the various polymer components arranged in relatively constantly positioned distinct zones across the cross-sectional area of the fiber and the various polymers are usually not continuous along the entire length of the fiber, instead usually forming fibrils or protofibrils which start and end at random. Thus, the term “unicomponent” is not intended to exclude fibers formed from a polymer or blends of one or more polymers to which small amounts of additives may be added for coloration, anti-static properties, lubrication, hydrophilicity, etc.
  • multicomponent fiber intended to mean a fiber prepared by melting the two or more fiber forming polymers in separate extruders and by directing the resulting multiple polymer flows into one spinneret with a plurality of distribution flow paths but spun together to form one fiber.
  • Multicomponent fibers are also sometimes referred to as conjugate or bicomponent fibers.
  • the polymers are arranged in substantially constantly positioned distinct segments or zones across the cross-section of the conjugate fibers and extend continuously along the length of the conjugate fibers.
  • the configuration of such a multicomponent fiber may be, for example, a sheath/core arrangement wherein one polymer is surrounded by another or may be a side by side arrangement, a pie arrangement or an "islands-in-the-sea" arrangement.
  • a multicomponent fiber may be prepared by extruding the sulfopolyester and one or more water non- dispersible polymers separately through a spinneret having a shaped or engineered transverse geometry such as, for example, an "islands-in-the-sea" or segmented pie configuration.
  • Multicomponent fibers typically, are staple, monofilament or multifilament fibers that have a shaped or round cross-section. Most fiber forms are heatset.
  • the fiber may include the various antioxidants, pigments, and additives as described herein.
  • Monofilament fibers generally range in size from about 15 to about 8000 denier per filament (abbreviated herein as "d/f ') ⁇ Our novel fibers typically will have d/f values in the range of about 40 to about 5000.
  • Monofilaments may be in the form of unicomponent or multicomponent fibers.
  • the multifilament fibers of our invention will preferably range in size from about 1.5 micrometers for melt blown webs, about 0.5 to about 50 d/f for staple fibers, and up to about 5000 d/f for monofilament fibers.
  • Multifilament fibers may also be used as crimped or uncrimped yarns and tows. Fibers used in melt blown web and melt spun fabrics may be produced in microdenier sizes.
  • microdenier is intended to mean a d/f value of 1 d/f or less.
  • the microdenier fibers of the instant invention typically have d/f values of 1 or less, 0.5 or less, or 0.1 or less.
  • Nanofibers can also be produced by electrostatic spinning.
  • the sulfopolyesters also are advantageous for the preparation of bicomponent and multicomponent fibers having a shaped cross section.
  • sulfopolyesters or blends of sulfopolyesters having a glass transition temperature (Tg) of at least 57 0 C are particularly useful for multicomponent fibers to prevent blocking and fusing of the fiber during spinning and take up.
  • Tg glass transition temperature
  • our invention provides a multicomponent fiber having shaped cross section, comprising:
  • n is an integer in the range of 2 to about 500;
  • the dicarboxylic acids, diols, sulfopolyester, sulfomonomers, and branching monomers residues are as described previously for other embodiments of the invention.
  • the sulfopolyester have a Tg of at least 57 0 C.
  • Further examples of glass transition temperatures that may be exhibited by the sulfopolyester or sulfopolyester blend of our multicomponent fiber are at least 6O 0 C, at least 65 0 C, at least 7O 0 C, at least 75 0 C, at least 8O 0 C, at least 85 0 C, and at least 9O 0 C.
  • blends of one or more sulfopolyesters may be used in varying proportions to obtain a sulfopolyester blend having the desired Tg.
  • the Tg of a sulfopolyester blend may be calculated by using a weighted average of the Tg' s of the sulfopolyester components.
  • sulfopolyester having a Tg of 48 0 C may be blended in a 25:75 wt:wt ratio with another sulfopolyester having Tg of 65 0 C to give a sulfopolyester blend having a Tg of approximately 61 0 C.
  • the water dispersible sulfopolyester component of the multicomponent fiber presents properties which allow at least one of the following:
  • the multicomponent fibers are heat settable to yield a stable, strong fabric.
  • a multicomponent fiber having a shaped cross section comprising:
  • the sulfopolyester utilized in these multicomponent fibers has a melt viscosity of generally less than about 12,000 poise.
  • the melt viscosity of the sulfopolyester is less than 10,000 poise, more preferably, less than 6,000, and most preferably, less than 4,000 poise measured at 240°C and 1 rad/sec shear rate.
  • the sulfopolyester exhibits a melt viscosity of between about 1000- 12000 poise, more preferably between 2000-6000 poise, and most preferably between 2500-4000 poise measured at 240 0 C and 1 rad/sec shear rate.
  • the samples Prior to determining the viscosity, the samples are dried at 60 0 C in a vacuum oven for 2 days.
  • the melt viscosity is measured on rheometer using a 25 mm diameter parallel-plate geometry at lmm gap setting. A dynamic frequency sweep is run at a strain rate range of 1 to 400 rad/sec and 10% strain amplitude. The viscosity is then measured at 240° C and strain rate of 1 rad/sec.
  • the level of sulfomonomer residues in the sulfopolyester polymers for use in accordance with this aspect of the present invention is generally less than about 25 mole %, and preferably, less than 20 mole %, reported as a percentage of the total diacid or diol residues in the sulfopolyester. More preferably, this level is between about 4 to about 20 mole %, even more preferably between about 5 to about 12 mole %, and most preferably between about 7 to about 10 mole %.
  • Sulfomonomers for use with the invention preferably have 2 functional groups and one or more sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof.
  • a sodiosulfo-isophthalic acid monomer is particularly preferred.
  • the sulfopolyester preferably comprises residues of one or more dicarboxylic acids, one or more diol residues wherein at least 25 mole %, based on the total diol residues, is a poly(ethylene glycol) having a structure
  • n is an integer in the range of 2 to about 500, and 0 to about 20 mole %, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof.
  • the sulfopolyester comprises from about 80-96 mole % dicarboxylic acid residues, from about 4 to about 20 mole % sulfomonomer residues, and 100 mole % diol residues (there being a total mole % of 200%, i.e., 100 mole % diacid and 100 mole % diol). More specifically, the dicarboxylic portion of the sulfopolyester comprises between about 60-80 mole % terephthalic acid, about 0-30 mole % isophthalic acid, and about 4-20 mole % 5- sodiosulfoisophthalic acid (5-SSIPA). The diol portion comprises from about 0-50 mole % diethylene glycol and from about 50-100 mole % ethylene glycol.
  • An exemplary formulation according to this embodiment of the invention is set forth subsequently.
  • the water non-dispersible component of the multicomponent fiber may comprise any of those water non-dispersible polymers described herein. Spinning of the fiber may also occur according to any method described herein. However, the improved rheological properties of multicomponent fibers in accordance with this aspect of the invention provide for enhanced drawings speeds.
  • the multicomponent extrudate is capable of being melt drawn to produce the multicomponent fiber, using any of the methods disclosed herein, at a speed of at least about 2000 m/min, more preferably at least about 3000 m/min, even more preferably at least about 4000 m/min, and most preferably at least about 4500 m/min.
  • melt drawing of the multicomponent extrudates at these speeds results in at least some oriented crystallinity in the water non-dispersible component of the multicomponent fiber. This oriented crystallinity can increase the dimensional stability of non- woven materials made from the multicomponent fibers during subsequent processing.
  • multicomponent extrudate Another advantage of the multicomponent extrudate is that it can be melt drawn to a multicomponent fiber having an as-spun denier of less than 6 deniers per filament.
  • Other ranges of multicomponent fiber sizes include an as-spun denier of less than 4 deniers per filament and less than 2.5 deniers per filament.
  • a multicomponent extrudate having a shaped cross section comprising:
  • the multicomponent fiber comprises a plurality of segments or domains of one or more water non-dispersible polymers immiscible with the sulfopolyester in which the segments or domains are substantially isolated from each other by the sulfopolyester intervening between the segments or domains.
  • substantially isolated is intended to mean that the segments or domains are set apart from each other to permit the segments domains to form individual fibers upon removal of the sulfopolyester.
  • the segments or domains may be touching each others as in, for example, a segmented pie configuration but can be split apart by impact or when the sulfopolyester is removed.
  • the ratio by weight of the sulfopolyester to water non-dispersible polymer component in the multicomponent fiber of the invention is generally in the range of about 60:40 to about 2:98 or, in another example, in the range of about 50:50 to about 5:95.
  • the sulfopolyester comprises 50% by weight or less of the total weight of the multicomponent fiber.
  • the segments or domains of multicomponent fiber may comprise one of more water non-dispersible polymers.
  • water non-dispersible polymers which may be used in segments of the multicomponent fiber include, but are not limited to, polyolefins, polyesters, polyamides, polylactides, polycaprolactone, polycarbonate, polyurethane, cellulose ester, and polyvinyl chloride.
  • the water non- dispersible polymer may be polyester such as poly(ethylene) terephthalate, poly(butylene) terephthalate, poly(cyclohexylene) cyclohexanedicarboxylate, poly(cyclohexylene) terephthalate, poly(trimethylene) terephthalate, and the like.
  • the water non-dispersible polymer can be biodistintegratable as determined by DIN Standard 54900 and/or biodegradable as determined by ASTM Standard Method, D6340-98. Examples of biodegradable polyesters and polyester blends are disclosed in U.S.
  • biodegradable as used herein in reference to the water non- dispersible polymers of the present invention, is understood to mean that the polymers are degraded under environmental influences such as, for example, in a composting environment, in an appropriate and demonstrable time span as defined, for example, by ASTM Standard Method, D6340-98, entitled "Standard Test Methods for Determining Aerobic Biodegradation of Radiolabeled Plastic Materials in an Aqueous or Compost Environment".
  • the water non-dispersible polymers of the present invention also may be "biodisintegratable", meaning that the polymers are easily fragmented in a composting environment as defined, for example, by DIN Standard 54900.
  • the biodegradable polymer is initially reduced in molecular weight in the environment by the action of heat, water, air, microbes and other factors. This reduction in molecular weight results in a loss of physical properties (tenacity) and often in fiber breakage.
  • the monomers and oligomers are then assimilated by the microbes. In an aerobic environment, these monomers or oligomers are ultimately oxidized to CO 2 , H 2 O, and new cell biomass. In an anaerobic environment, the monomers or oligomers are ultimately converted to CO 2 , H 2 , acetate, methane, and cell biomass.
  • water non-dispersible polymer may be an aliphatic-aromatic polyester, abbreviated herein as "AAPE".
  • aliphatic-aromatic polyester means a polyester comprising a mixture of residues from aliphatic or cycloaliphatic dicarboxylic acids or diols and aromatic dicarboxylic acids or diols.
  • non-aromatic as used herein with respect to the dicarboxylic acid and diol monomers of the present invention, means that carboxyl or hydroxyl groups of the monomer are not connected through an aromatic nucleus.
  • adipic acid contains no aromatic nucleus in its backbone, i.e., the chain of carbon atoms connecting the carboxylic acid groups, thus is “non-aromatic".
  • aromatic means the dicarboxylic acid or diol contains an aromatic nucleus in the backbone such as, for example, terephthalic acid or 2,6-naphthalene dicarboxylic acid.
  • Non-aromatic is intended to include both aliphatic and cycloaliphatic structures such as, for example, diols and dicarboxylic acids, which contain as a backbone a straight or branched chain or cyclic arrangement of the constituent carbon atoms which may be saturated or paraffinic in nature, unsaturated, i.e., containing non-aromatic carbon-carbon double bonds, or acetylenic, i.e., containing carbon- carbon triple bonds.
  • diols and dicarboxylic acids which contain as a backbone a straight or branched chain or cyclic arrangement of the constituent carbon atoms which may be saturated or paraffinic in nature, unsaturated, i.e., containing non-aromatic carbon-carbon double bonds, or acetylenic, i.e., containing carbon- carbon triple bonds.
  • non-aromatic is intended to include linear and branched, chain structures (referred to herein as “aliphatic”) and cyclic structures (referred to herein as “alicyclic” or “cycloaliphatic”).
  • aliphatic chain structures
  • cyclic cycloaliphatic
  • the difunctional carboxylic acid typically is a aliphatic dicarboxylic acid such as, for example, adipic acid, or an aromatic dicarboxylic acid such as, for example, terephthalic acid.
  • the difunctional hydroxyl compound may be cycloaliphatic diol such as, for example, 1,4-cyclohexanedimethanol, a linear or branched aliphatic diol such as, for example, 1 ,4-butanediol, or an aromatic diol such as, for example, hydroquinone.
  • cycloaliphatic diol such as, for example, 1,4-cyclohexanedimethanol
  • a linear or branched aliphatic diol such as, for example, 1 ,4-butanediol
  • an aromatic diol such as, for example, hydroquinone.
  • the AAPE may be a linear or branched random copolyester and/or chain extended copolyester comprising diol residues which comprise the residues of one or more substituted or unsubstituted, linear or branched, diols selected from aliphatic diols containing 2 to about 8 carbon atoms, polyalkylene ether glycols containing 2 to 8 carbon atoms, and cycloaliphatic diols containing about 4 to about 12 carbon atoms.
  • the substituted diols typically, will comprise 1 to about 4 substituents independently selected from halo, C 6 -Ci 0 aryl, and C1-C4 alkoxy.
  • diols which may be used include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethyl-l,3-propanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol, diethylene glycol, 2,2,4- trimethyl-l,6-hexanediol, thiodiethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-l,3-cyclobutanediol, Methylene glycol, and tetraethylene glycol with the preferred diols comprising one or more diols selected from 1 ,4-butanediol; 1,3-propanediol;
  • the AAPE also comprises diacid residues which contain about 35 to about 99 mole%, based on the total moles of diacid residues, of the residues of one or more substituted or unsubstituted, linear or branched, non-aromatic dicarboxylic acids selected from aliphatic dicarboxylic acids containing 2 to about 12 carbon atoms and cycloaliphatic acids containing about 5 to about 10 carbon atoms.
  • the substituted non-aromatic dicarboxylic acids will typically contain 1 to about 4 substituents selected from halo, C 6 -C 10 aryl, and Ci-C 4 alkoxy.
  • Non-limiting examples of non-aromatic diacids include malonic, succinic, glutaric, adipic, pimelic, azelaic, sebacic, fumaric, 2,2-dimethyl glutaric, suberic, 1,3- cyclopentanedicarboxylic, 1,4-cyclohexanedicarboxylic, 1,3- cyclohexanedicarboxylic, diglycolic, itaconic, maleic, and 2,5-norbornane- dicarboxylic.
  • the AAPE comprises about 1 to about 65 mole%, based on the total moles of diacid residues, of the residues of one or more substituted or unsubstituted aromatic dicarboxylic acids containing 6 to about 10 carbon atoms.
  • substituted aromatic dicarboxylic acids they will typically contain 1 to about 4 substituents selected from halo, C 6 -C I0 aryl, and Ci-C 4 alkoxy.
  • Non-limiting examples of aromatic dicarboxylic acids which may be used in the AAPE of our invention are terephthalic acid, isophthalic acid, salts of 5-sulfoisophthalic acid, and 2,6- naphthalenedicarboxylic acid. More preferably, the non-aromatic dicarboxylic acid will comprise adipic acid, the aromatic dicarboxylic acid will comprise terephthalic acid, and the diol will comprise 1,4-butanediol.
  • compositions for the AAPE' s of our invention are those prepared from the following diols and dicarboxylic acids (or polyester-forming equivalents thereof such as diesters) in the following mole percentages, based on 100 mole percent of a diacid component and 100 mole percent of a diol component:
  • glutaric acid about 30 to about 75%); terephthalic acid (about 25 to about 70%); 1,4-butanediol (about 90 to 100%); and modifying diol (0 about 10%);
  • succinic acid about 30 to about 95%
  • terephthalic acid about 5 to about 70%
  • 1,4-butanediol about 90 to 100%
  • modifying diol (0 to about 10%)
  • adipic acid about 30 to about 75%); terephthalic acid (about 25 to about 70%); 1,4-butanediol (about 90 to 100%); and modifying diol (0 to about 10%).
  • the modifying diol preferably is selected from 1 ,4-cyclohexanedimethanol, triethylene glycol, polyethylene glycol and neopentyl glycol.
  • the most preferred AAPE's are linear, branched or chain extended copolyesters comprising about 50 to about 60 mole percent adipic acid residues, about 40 to about 50 mole percent terephthalic acid residues, and at least 95 mole percent 1 ,4-butanediol residues.
  • the adipic acid residues comprise about 55 to about 60 mole percent
  • the terephthalic acid residues comprise about 40 to about 45 mole percent
  • the diol residues comprise about 95 mole percent 1 ,4-butanediol residues.
  • Such compositions are commercially available under the trademark EASTAR BIO ® copolyester from Eastman Chemical Company, Kingsport, TN, and under the trademark ECOFLEX from BASF Corporation.
  • AAPE's include a poly(tetra- methylene glutarate-co-terephthalate) containing (a) 50 mole percent glutaric acid residues, 50 mole percent terephthalic acid residues, and 100 mole percent 1,4- butanediol residues, (b) 60 mole percent glutaric acid residues, 40 mole percent terephthalic acid residues, andlOO mole percent 1 ,4-butanediol residues or (c) 40 mole percent glutaric acid residues, 60 mole percent terephthalic acid residues, and 100 mole percent 1 ,4-butanediol residues; a poly(tetramethylene succinate-co- terephthalate) containing (a) 85 mole percent succinic acid residues, 15 mole percent terephthalic acid residues, and 100 mole percent 1 ,4-butanediol residues or (b) 70 mole percent succinic
  • the AAPE preferably comprises from about 10 to about 1,000 repeating units and preferably, from about 15 to about 600 repeating units.
  • the AAPE may have an inherent viscosity of about 0.4 to about 2.0 dL/g, or more preferably about 0.7 to about 1.6 dL/g, as measured at a temperature of 25°C using a concentration of 0.5 gram copoly ester in 100 ml of a 60/40 by weight solution of phenol/tetrachloroethane.
  • the AAPE may contain the residues of a branching agent.
  • the mole percentage ranges for the branching agent are from about 0 to about 2 mole%, preferably about 0.1 to about 1 mole%, and most preferably about 0.1 to about 0.5 mole% based on the total moles of diacid or diol residues (depending on whether the branching agent contains carboxyl or hydroxyl groups).
  • the branching agent preferably has a weight average molecular weight of about 50 to about 5000, more preferably about 92 to about 3000, and a functionality of about 3 to about 6.
  • the branching agent may be the esterified residue of a polyol having 3 to 6 hydroxyl groups, a polycarboxylic acid having 3 or 4 carboxyl groups (or ester- forming equivalent groups) or a hydroxy acid having a total of 3 to 6 hydroxyl and carboxyl groups.
  • the AAPE may be branched by the addition of a peroxide during reactive extrusion.
  • Each segment of the water non-dispersible polymer may be different from others in fineness and may be arranged in any shaped or engineered cross-sectional geometry known to persons skilled in the art.
  • the sulfopolyester and a water non-dispersible polymer may be used to prepare a bicomponent fiber having an engineered geometry such as, for example, a side-by-side, "islands-in-the-sea", segmented pie, other splitables, sheath/core, or other configurations known to persons skilled in the art.
  • Other multicomponent configurations are also possible. Subsequent removal of a side, the "sea", or a portion of the "pie” can result in very fine fibers.
  • the process of preparing bicomponent fibers also is well known to persons skilled in the art.
  • the sulfopolyester fibers of this invention may be present in amounts of about 10 to about 90 weight% and will generally be used in the sheath portion of sheath/core fibers.
  • the resulting bicomponent or multicomponent fiber is not completely water-dispersible.
  • Side by side combinations with significant differences in thermal shrinkage can be utilized for the development of a spiral crimp. If crimping is desired, a saw tooth or stuffer box crimp is generally suitable for many applications.
  • the second polymer component is in the core of a sheath/core configuration, such a core optionally may be stabilized.
  • the sulfopolyesters are particularly useful for fibers having an "islands-in-the- sea” or “segmented pie” cross section as they only requires neutral or slightly acidic (i.e., "soft” water) to disperse, as compared to the caustic-containing solutions that are sometimes required to remove other water dispersible polymers from multicomponent fibers.
  • soft water as used in this disclosure means that the water has up to 5 grains per gallon as CaCO 3 (1 grain of CaCO 3 per gallon is equivalent to 17.1 ppm).
  • a multicomponent fiber comprising:
  • n is an integer in the range of 2 to about 500;
  • the dicarboxylic acids, diols, sulfopolyester, sulfomonomers, branching monomers residues, and water non-dispersible polymers are as described previously.
  • sulfopolyester have a Tg of at least 57 0 C.
  • the sulfopolyester may be a single sulfopolyester or a blend of one or more sulfopolyester polymers.
  • glass transition temperatures that may be exhibited by the sulfopolyester or sulfopolyester blends are at least 65 0 C, at least 7O 0 C, at least 75 0 C, at least 85 0 C, and at least 9O 0 C.
  • the sulfopolyester may comprise about 75 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid and about 25 to about 95 mole% of a residue of diethylene glycol.
  • examples of the water non-dispersible polymers are polyolefins, polyesters, polyamides, polylactides, polycaprolactones, polycarbonates, polyurethanes, cellulose esters, and polyvinyl chlorides.
  • the water non- dispersible polymer may be biodegradable or biodisintegratable.
  • the water non-dispersible polymer may be an aliphatic-aromatic polyester as described previously.
  • Our novel multicomponent fiber may be prepared by any number of methods known to persons skilled in the art.
  • the present invention thus provides a process for a multicomponent fiber having a shaped cross section comprising: spinning a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 57 0 C and one or more water non-dispersible polymers immiscible with the sulfopolyester into a fiber, the sulfopolyester comprising:
  • n is an integer in the range of 2 to about 500;
  • the multicomponent fiber may be prepared by melting the sulfopolyester and one or more water non-dispersible polymers in separate extruders and directing the individual polymer flows into one spinneret or extrusion die with a plurality of distribution flow paths such that the water non-dispersible polymer component form small segments or thin strands which are substantially isolated from each other by the intervening sulfopolyester.
  • the cross section of such a fiber may be, for example, a segmented pie arrangement or an islands-in-the-sea arrangement.
  • the sulfopolyester and one or more water non-dispersible polymers are separately fed to the spinneret orifices and then extruded in sheath-core form in which the water non-dispersible polymer forms a "core" that is substantially enclosed by the sulfopolyester "sheath" polymer.
  • the orifice supplying the "core" polymer is in the center of the spinning orifice outlet and flow conditions of core polymer fluid are strictly controlled to maintain the concentricity of both components when spinning. Modifications in spinneret orifices enable different shapes of core and/or sheath to be obtained within the fiber cross- section.
  • a multicomponent fiber having a side-by-side cross section or configuration may be produced by coextruding the water dispersible sulfopolyester and water non-dispersible polymer through orifices separately and converging the separate polymer streams at substantially the same speed to merge side-by-side as a combined stream below the face of the spinneret; or (2) by feeding the two polymer streams separately through orifices, which converge at the surface of the spinneret, at substantially the same speed to merge side-by-side as a combined stream at the surface of the spinneret.
  • the velocity of each polymer stream, at the point of merge, is determined by its metering pump speed, the number of orifices, and the size of the orifice.
  • the dicarboxylic acids, diols, sulfopolyester, sulfomonomers, branching monomers residues, and water non-dispersible polymers are as described previously.
  • the sulfopolyester has a glass transition temperature of at least 57 0 C. Further examples of glass transition temperatures that may be exhibited by the sulfopolyester or sulfopolyester blend are at least 65 0 C, at least 7O 0 C, at least 75 0 C, at least 85 0 C, and at least 9O 0 C.
  • the sulfopolyester may comprise about 50 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid, based on the total acid residues; and about 4 to about 30 mole%, based on the total acid residues, of a residue of sodiosulfoisophthalic acid; and 0 to about 20 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof.
  • the sulfopolyester may comprise about 75 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid and about 25 to about 95 mole% of a residue of diethylene glycol.
  • examples of the water non-dispersible polymers are polyolefins, polyesters, polyamides, polylactides, polycaprolactone, polycarbonate, polyurethane, and polyvinyl chloride.
  • the water non-dispersible polymer may be biodegradable or biodisintegratable.
  • the water non-dispersible polymer may be an aliphatic-aromatic polyester as described previously. Examples of shaped cross sections include, but are not limited to, islands-in-the-sea, side-by-side, sheath- core, or segmented pie configurations.
  • a process for making a multicomponent fiber having a shaped cross section comprising: spinning at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with the sulfopolyester to produce a multicomponent fiber, wherein the multicomponent fiber has a plurality of domains comprising the water non-dispersible polymers and the domains are substantially isolated from each other by the sulfopolyester intervening between the domains; wherein the water dispersible sulfopolyester exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprising less than about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residues; and wherein the multicomponent fiber has an as-spun de
  • a process for making a multicomponent fiber having a shaped cross section comprising:
  • (B) melt drawing the multicomponent extrudate at a speed of at least about 2000 m/min to produce the multicomponent fiber.
  • the process includes the step of melt drawing the multicomponent extrudate at a speed of at least about 2000 m/min, more preferably, at least about 3000 m/min, and most preferably at least 4500 m/min.
  • the fibers are quenched with a cross flow of air whereupon the fibers solidify.
  • Various finishes and sizes may be applied to the fiber at this stage.
  • the cooled fibers typically, are subsequently drawn and wound up on a take up spool.
  • Other additives may be incorporated in the finish in effective amounts like emulsifiers, antistatics, antimicrobials, antifoams, lubricants, thermostabilizers, UV stabilizers, and the like.
  • the drawn fibers may be textured and wound-up to form a bulky continuous filament.
  • This one-step technique is known in the art as spin-draw- texturing.
  • Other embodiments include flat filament (non-textured) yarns, or cut staple fiber, either crimped or uncrimped.
  • the sulfopolyester may be later removed by dissolving the interfacial layers or pie segments and leaving the smaller filaments or microdenier fibers of the water non- dispersible polymer(s).
  • Our invention thus provides a process for microdenier fibers comprising:
  • A spinning a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 57 0 C and one or more water non-dispersible polymers immiscible with the sulfopolyester into multicomponent fibers, the sulfopolyester comprising:
  • n is an integer in the range of 2 to about 500;
  • the multicomponent fiber is contacted with water at a temperature of about 25 0 C to about 100 0 C, preferably about 50 0 C to about 8O 0 C for a time period of from about 10 to about 600 seconds whereby the sulfopolyester is dissipated or dissolved.
  • the remaining water non-dispersible polymer microfibers typically will have an average fineness of 1 d/f or less, typically, 0.5 d/f or less, or more typically, 0.1 d/f or less.
  • Typical applications of these remaining water non-dispersible polymer microfibers include nonwoven fabrics, such as, for example, artificial leathers, suedes, wipes, and filter media.
  • Filter media produce from these microfibers can be utilized to filter air or liquids.
  • Filter media for liquids include, but are not limited to, water, bodily fluids, solvents, and hydrocarbons.
  • the ionic nature of sulfopolyesters also results in advantageously poor "solubility" in saline media, such as body fluids. Such properties are desirable in personal care products and cleaning wipes that are flushable or otherwise disposed in sanitary sewage systems.
  • Selected sulfopolyesters have also been utilized as dispersing agents in dye baths and soil redeposition preventative agents during laundry cycles.
  • a process for making microdenier fibers comprising spinning at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with the water dispersible sulfopolyester into multicomponent fibers, wherein said multicomponent fibers have a plurality of domains comprising said water non- dispersible polymers wherein the domains are substantially isolated from each other by the sulfopolyester intervening between the domains; wherein the fiber has an as- spun denier of less than about 6 denier per filament; wherein the water dispersible sulfopolyester exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprising less than about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residue
  • microdenier fibers comprising:
  • melt drawing of the multicomponent extrudates at a speed of at least about 2000 m/min, more preferably at least about 3000 m/min, and most preferably at least 4500 m/min.
  • the water used to remove the sulfopolyester from the multicomponent fibers be above room temperature, more preferably the water is at least about 45 °C, even more preferably at least about 60°C, and most preferably at least about 80°C.
  • another process is provided to produce water non-dispersible polymer microfibers.
  • the process comprises: a) cutting a multicomponent fiber into cut multicomponent fibers; b) contacting a fiber-containing feedstock with water to produce a fiber mix slurry; wherein said fiber-containing feedstock comprises cut multicomponent fibers; c) heating said fiber mix slurry to produce a heated fiber mix slurry; d) optionally, mixing said fiber mix slurry in a shearing zone; e) removing at least a portion of the sulfopolyester from said multicomponent fiber to produce a slurry mixture comprising a sulfopolyester dispersion and the water non-dispersible polymer microfibers; and f) separating the water non-dispersible polymer microfibers from said slurry mixture.
  • the multicomponent fiber can be cut into any length that can be utilized to produce nonwoven articles.
  • the multicomponent fiber is cut into lengths ranging from about lmm to about 50 mm.
  • the multicomponent fiber can be cut into a mixture of different lengths.
  • the fiber-containing feedstock can comprise any other type of fiber that is useful in the production of nonwoven articles.
  • the fiber- containing feedstock further comprises at least one fiber selected from the group consisting of cellulosic fiber pulp, glass fiber, polyester fibers, nylon fibers, polyolefin fibers, rayon fibers and cellulose ester fibers.
  • the fiber-containing feedstock is mixed with water to produce a fiber mix slurry.
  • the water utilized can be soft water or deionized water.
  • Soft water has been previously defined in this disclosure.
  • at least one water softening agent may be used to facilitate the removal of the water-dispersible sulfopolyester from the multicomponent fiber. Any water softening agent known in the art can be utilized.
  • the water softening agent is a chelating agent or calcium ion sequestrant.
  • Applicable chelating agents or calcium ion sequestrants are compounds containing a plurality of carboxylic acid groups per molecule where the carboxylic groups in the molecular structure of the chelating agent are separated by 2 to 6 atoms.
  • Tetrasodium ethylene diamine tetraacetic acid (EDTA) is an example of the most common chelating agent, containing four carboxylic acid moieties per molecular structure with a separation of 3 atoms between adjacent carboxylic acid groups.
  • Poly acrylic acid, sodium salt is an example of a calcium sequestrant containing carboxylic acid groups separated by two atoms between carboxylic groups.
  • Sodium salts of maleic acid or succinic acid are examples of the most basic chelating agent compounds.
  • applicable chelating agents include compounds which have in common the presence of multiple carboxylic acid groups in the molecular structure where the carboxylic acid groups are separated by the required distance (2 to 6 atom units) which yield a favorable steric interaction with di- or multi- valent cations such as calcium which cause the chelating agent to preferentially bind to di- or multi valent cations.
  • Such compounds include, but are not limited to, diethylenetriaminepentaacetic acid; diethylenetriamine- N,N,N',N',N"-pentaacetic acid; pentetic acid; N,N-bis(2-(bis- (carboxymethyl)amino)ethyl)-glycine; diethylenetriamine pentaacetic acid; [[(carboxymethyl)imino]bis(ethylenenitrilo)]-tetra-acetic acid; edetic acid; ethylenedinitrilotetraacetic acid; EDTA, free base; EDTA free acid; ethylenediamine- N,N,N',N'-tetraacetic acid; hampene; versene; N 3 N'- 1 ,2-ethane diylbis-(N- (carboxymethyl)glycine); ethylenediamine tetra-acetic acid; N 5 N- bis(carboxymethyl)glycine; triglycollamic acid; tri
  • the amount of water softening agent needed depends on the hardness of the water utilized in terms of Ca + * and other multivalent ions.
  • the fiber mix slurry is heated to produce a heated fiber mix slurry.
  • the temperature is that which is sufficient to remove a portion of the sulfopolyester from the multicomponent fiber.
  • the fiber mix slurry is heated to a temperature ranging from about 50 ° C to about 100 ° C. Other temperature ranges are from about 70 ° C to about 100 ° C, about 80 ° C to about 100 ° C, and about 90 ° C to about 100 ° C.
  • the fiber mix slurry is mixed in a shearing zone.
  • the amount of mixing is that which is sufficient to disperse and remove a portion of the water dispersible sulfopolyester from the multicomponent fiber and separate the water non- dispersible polymer microfibers.
  • 90% of the sulfopolyester is removed.
  • 95% of the sulfopolyester is removed, and in yet another embodiment, 98% or greater of the sulfopolyester is removed.
  • the shearing zone can comprise any type of equipment that can provide shearing action necessary to disperse and remove a portion of the water dispersible sulfopolyester from the multicomponent fiber and separate the water non-dispersible polymer microfibers.
  • examples of such equipment include, but is not limited to, pulpers and refiners.
  • the water dispersible sulfopolyester in the multicomponent fiber after contact with water and heating disperse and separate from the water non-dispersible polymer fiber to produce a slurry mixture comprising a sulfopolyester dispersion and the water non-dispersible polymer microfibers.
  • the water non-dispersible polymer microfibers can then be separated from the sulfopolyester dispersion by any means known in the art.
  • the slurry mixture can be routed through separating equipment, such as for example, screens and filters.
  • the water non-dispersible polymer microfibers may be washed once or numerous times to remove more of the water-dispersible sulfopolyester.
  • the removal of the water-dispersible sulfopolyester can be determined by physical observation of the slurry mixture.
  • the water utilized to rinse the water non- dispersible polymer microfibers is clear if the water-dispersible sulfopolyester has been mostly removed. If the water-dispersible sulfopolyester is still being removed, the water utilized to rinse the water non-dispersible polymer microfibers can be milky. Further, if water-dispersible sulfopolyester remains on the water non- dispersible polymer microfibers, the microfibers can be somewhat sticky to the touch.
  • the water-dispersible sulfopolyester can be recovered from the sulfopolyester dispersion by any method known in the art.
  • a water non-dispersible polymer microfiber comprising at least one water non-dispersible polymer wherein the water non-dispersible polymer microfiber has an equivalent diameter of less than 5 microns and length of less than 25 millimeters.
  • This water non-dispersible polymer microfiber is produced by the processes previously described to produce microfibers.
  • the water non-dispersible polymer microfiber has an equivalent diameter of less than 3 microns and length of less than 25 millimeters.
  • the water non-dispersible polymer microfiber has an equivalent diameter of less than 5 microns or less than 3 microns.
  • the water non-dispersible polymer microfiber can have lengths of less than 12 millimeters; less than 10 millimeters, less than 6.5 millimeters, and less than 3.5 millimeters.
  • the domains or segments in the, multicomponent fiber once separated yield the water non-dispersible polymer microfibers.
  • the instant invention also includes a fibrous article comprising the water- dispersible fiber, the multicomponent fiber, microdenier fibers, or water non- dispersible polymer microfibers described hereinabove.
  • fibrous article is understood to mean any article having or resembling fibers.
  • Non-limiting examples of fibrous articles include multifilament fibers, yarns, cords, tapes, fabrics, wet-laid webs, dry-laid webs, melt blown webs, spunbonded webs, thermobonded webs, hydroentangled webs, nonwoven webs and fabrics, and combinations thereof; items having one or more layers of fibers, such as, for example, multilayer nonwovens, laminates, and composites from such fibers, gauzes, bandages, diapers, training pants, tampons, surgical gowns and masks, feminine napkins; and the like.
  • the water non-dispersible microdfibers can be utilized in filter media for air filtration, liquid filtration, filtration for food preparation, filtration for medical applications, and for paper making processes and paper products.
  • the fibrous articles may include replacement inserts for various personal hygiene and cleaning products.
  • the fibrous article of the present invention may be bonded, laminated, attached to, or used in conjunction with other materials which may or may not be water-dispersible.
  • the fibrous article for example, a nonwoven fabric layer, may be bonded to a flexible plastic film or backing of a water non-dispersible material, such as polyethylene.
  • a water non-dispersible material such as polyethylene.
  • Such an assembly for example, could be used as one component of a disposable diaper.
  • the fibrous article may result from overblowing fibers onto another substrate to form highly assorted combinations of engineered melt blown, spunbond, film, or membrane structures.
  • the fibrous articles of the instant invention include nonwoven fabrics and webs.
  • a nonwoven fabric is defined as a fabric made directly from fibrous webs without weaving or knitting operations.
  • the Textile Institue defines nonwovens as textile structures made directly from fibre rather than yarn. These fabrics are normally made from continuous filments or from fibre webs or batts strengthened by bonding using various techniques, which include, but are not limited to, adhesive bonding, mechanical interlocking by needling or fluid jet entanglement, thermal bonding, and stitch bonding.
  • the multicomponent fiber of the present invention may be formed into a fabric by any known fabric forming process.
  • the resulting fabric or web may be converted into a microdenier fiber web by exerting sufficient force to cause the multicomponent fibers to split or by contacting the web with water to remove the sulfopolyester leaving the remaining microdenier fibers behind.
  • Our invention thus provides a process for a microdenier fiber web, comprising:
  • A spinning a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 57 0 C and one or more water non-dispersible polymers immiscible with the sulfopolyester into multicomponent fibers, the sulfopolyester comprising:
  • n is an integer in the range of 2 to about 500;
  • the multicomponent fibers have a plurality of segments comprising the water non-dispersible polymers wherein the segments are substantially isolated from each other by the sulfopolyester intervening between the segments; and the fiber contains less than 10 weight percent of a pigment or filler, based on the total weight of the fiber; (B) overlapping and collecting the multicomponent fibers of Step A to form a nonwoven web; and
  • a process for a microdenier fiber web which comprises:
  • Step B collecting said multicomponent fibers of Step A) to form a non-woven web
  • a process for a microdenier fiber web which comprises:
  • Step (B) melt drawing said multicomponent extrudates at a speed of at least about 2000 m/min to produce multicomponent fibers;
  • the process also preferably comprises prior to Step (C) the step of hydroentangling the multicomponent fibers of the non- woven web. It is also preferable that the hydroentangling step results in a loss of less than about 20 wt. % of the sulfopolyester contained in the multicomponent fibers, more preferably this loss is less than 15 wt. %, and most preferably is less than 10 wt. %.
  • the water used during this process preferably has a temperature of less than about 45 °C, more preferably less than about 35°C, and most preferably less than about 30°C.
  • the water used during hydroentanglement be as close to room temperature as possible to minimize loss of sulfopolyester from the multicomponent fibers.
  • removal of the sulfopolyester polymer during Step (C) is preferably carried out using water having a temperature of at least about 45°C, more preferably at least about 60°C, and most preferably at least about 80°C.
  • the non-woven web may under go a heat setting step comprising heating the non- woven web to a temperature of at least about 100°C, and more preferably at least about 12O 0 C.
  • the heat setting step relaxes out internal fiber stresses and aids in producing a dimensionally stable fabric product. It is preferred that when the heat set material is reheated to the temperature to which it was heated during the heat setting step that it exhibits surface area shrinkage of less than about 5% of its original surface area. More preferably, the shrinkage is less than about 2% of the original surface area, and most preferably the shrinkage is less than about 1%.
  • the sulfopolyester used in the multicomponent fiber can be any of those described herein, however, it is preferable that the sulfopolyester have a melt viscosity of less than about 6000 poise measured at 240°C at a strain rate of 1 rad/sec and comprise less than about 12 mole %, based on the total repeating units, of residues of at least one sulfomonomer.
  • melt viscosity less than about 6000 poise measured at 240°C at a strain rate of 1 rad/sec
  • residues of at least one sulfomonomer are previously described herein.
  • the inventive method preferably comprises the step of drawing the multicomponent fiber at a fiber velocity of at least 2000 m/min, more preferably at least about 3000 m/min, even more preferably at least about 4000 m/min, and most preferably at least about 5000 m/min.
  • nonwoven articles comprising water non-dispersible polymer microfibers
  • the nonwoven article comprises water non-dispersible polymer microfibers and is produced by a process selected from the group consisting of a dry-laid process and a wet-laid process. Multicomponent fibers and processes for producing water non-dispersible polymer microfibers were previously disclosed in the specification.
  • At least 1% of the water non-dispersible polymer microfiber is contained in the nonwoven article.
  • Other amounts of water non-dispersible polymer microfiber contained in the nonwoven article are at least 10%, at least 25%, and at least 50%.
  • the nonwoven article can further comprise at least one other fiber.
  • the other fiber can be any that is known in the art depending on the type of nonwoven article to be produced.
  • the other fiber can be selected from the group consisting cellulosic fiber pulp, glass fiber, polyester fibers, nylon fibers, polyolefin fibers, rayon fibers cellulose ester fibers, and mixtures thereof.
  • the nonwoven article can also further comprise at least one additive.
  • Additives include, but are not limited to, starches, fillers, and binders. Other additives are discussed in other sections of this disclosure.
  • manufacturing processes to produce these nonwoven articles from water non-dispersible microfibers produced from multicomponent fibers can be split into the following groups: dry-laid webs, wet-laid webs, and combinations of these processes with each other or other nonwoven processes.
  • dry-laid nonwoven articles are made with staple fiber processing machinery which is designed to manipulate fibers in the dry state. These include mechnical processes, such as, carding, aerodynamic, and other air-laid routes. Also included in this category are nonwoven articles made from filaments in the form of tow, and fabrics composed of staple fibers and stitching filaments or yards i.e. stitchbonded nonwovens. Carding is the process of disentangling, cleaning, and intermixing fibers to make a web for further processing into a nonwoven article. The process predominantly aligns the fibers which are held together as a web by mechanical entanglement and fiber-fiber friction.
  • Cards are generally configured with one or more main cylinders, roller or stationary tops, one or more doffers, or various combinations of these principal components.
  • a card On example of a card is a roller card.
  • the carding action is the combing or working of the water non-dispersible polymer microfibers between the points of the card on a series of interworking card rollers.
  • Other types of cards include woolen, cotton, and random cards. Garnetts can also be used to align these fibers.
  • the water non-dispersible polymer microfibers in the dried-laid process can also be aligned by air-laying. These fibers are directed by air current onto a collector which can be a flat conveyor or a drum.
  • Extrusion-formed webs can also be produced from the multicomponents fibers of this invention. Examples include spunbonded and melt-blown. Extrusion technology is used to produce spunbond, meltblown, and porous-film nonwoven articles. These nonwoven articles are made with machinery associated with polymer extrusion methods such as melt spinning, film casting, and extrusion coating. The nonwoven article is then contacted with water to remove the water dispersible sulfopolyester thus producing a nonwoven article comprising water non-dispersible polymer microfibers.
  • the water dispersible sulfopolyester and water non- dispersible polymer are transformed directly to fabric by extruding multicomponent filaments, orienting them as bundles or groupings, layering them on a conveying screen, and interlocking them.
  • the interlocking can be conducted by thermal fusion, mechnical entanglement, hydroentangling, chemical binders, or combinations of these processes.
  • Meltblown fabrics are also made directly from the water dispersible sulfopolyester and the water non-dispersible polymer.
  • the polymers are melted and extruded. As soon as the melt passes through the extrusion orifice, it is blown with air at high temperature. The air stream attenuates and solidifies the molten polymers.
  • the multicomponent fibers can then be separated from the air stream as a web and compressed between heated rolls.
  • Combined spunbond and meltbond processes can also be utilized to produce nonwoven articles.
  • Wet laid processes involve the use of papermaking technology to produce nonwoven articles. These nonwoven articles are made with machinery associated with pulp fiberizing, such as hammer mills, and paperforming. For example, slurry pumping onto continous screens which are designed to manipulate short fibers in a fluid.
  • water non-dispersible polymer microfibers are suspended in water, brought to a forming unit where the water is drained off through a forming screen, and the fibers are deposited on the screen wire.
  • water non-dispersible polymer microfibers are dewatered on a sieve or a wire mesh which revolves at the beginning of hydraulic formers over dewatering modules (suction boxes, foils and curatures) at high speeds of up to 1500 meters per minute.
  • dewatering modules suction boxes, foils and curatures
  • the sheet is then set on this wire and dewatering proceeds to a solid content of approximately 20-30%.
  • the sheet can then be pressed and dried.
  • a process comprising: a) optionally, rinsing the water non-dispersible polymer microfibers with water ; b) adding water to the water non-dispersible polymer microfibers to produce a water non-dispersible polymer microf ⁇ ber slurry; c) optionally, adding other fibers and /or additives to water non-dispersible polymer microfibers or slurry; and d) transferring the water non-dispersible polymer microfibers containing slurry to a wet-laid nonwoven zone to produce the nonwoven article.
  • Step a the number of rinses depends on the particular use chosen for the water non-dispersible polymer microfibers.
  • Step b) sufficient water is added to the microfibers to allow them to be routed to the wet-laid nonwoven zone.
  • the wet-laid nonwoven zone comprises any equipment known in the art to produce wet-laid nonwoven articles.
  • the wet- laid nonwoven zone comprises at least one screen, mesh, or sieve in order to remove the water from the water non-dispersible polymer microfiber slurry.
  • the water non-dispersible polymer microfiber slurry is mixed prior to transferring to the wet-laid nonwoven zone.
  • Web-bonding processes can also be utilized to produce nonwoven articles. These can be split into chemical and physical processes. Chemical bonding refers to the use of water-based and solvent-based polymers to bind together the fibers and/or fibrous webs. These binders can be applied by saturation, impregnation, spraying, printing, or application as a foam. Physical bonding processes include thermal processes such as calendaring and hot air bonding, and mechanical processes such as needling and hydroentangling. Needling or needle-punching processes mechanically interlock the fibers by physically moving some of the fibers from a near-horizontal to a near-vertical position. Needle-punching can be conducted by a needleloom. A needleloom generally contains a web-feeding mechanism, a needle beam which comprises a needleboard which holds the needles, a stripper plate, a bed plate, and a fabric take-up mechanism.
  • Stitchbonding is a mechanical bonding method that uses knitting elements, with or without yarn, to interlock the fiber webs.
  • stitchbonding machines include, but are not limited to, Maliwatt, Arachne, Malivlies, and Arabeva.
  • the nonwoven article can be held together by 1) mechanical fiber cohesion and interlocking in a web or mat; 2) various techniques of fusing of fibers, including the use of binder fibers, utilizing the thermoplastic properties of certain polymers and polymer blends; 3) use of a binding resin such as starch, casein, a cellulose derivative, or a synthetic resin, such as an acrylic latex or urethane; 4) powder adhesive binders; or 5) combinations thereof.
  • the fibers are often deposited in a random manner, although orientation in one direction is possible, followed by bonding using one of the methods described above.
  • the fibrous articles of our invention further also may comprise one or more layers of water-dispersible fibers, multicomponent fibers, or microdenier fibers.
  • the fiber layers may be one or more nonwoven fabric layers, a layer of loosely bound overlapping fibers, or a combination thereof.
  • the fibrous articles may include personal and health care products such as, but not limited to, child care products, such as infant diapers; child training pants; adult care products, such as adult diapers and adult incontinence pads; feminine care products, such as feminine napkins, panty liners, and tampons; wipes; fiber-containing cleaning products; medical and surgical care products, such as medical wipes, tissues, gauzes, examination bed coverings, surgical masks, gowns, bandages, and wound dressings; fabrics; elastomeric yarns, wipes, tapes, other protective barriers, and packaging material.
  • the fibrous articles may be used to absorb liquids or may be pre-moistened with various liquid compositions and used to deliver these compositions to a surface.
  • Non-limiting examples of liquid compositions include detergents; wetting agents; cleaning agents; skin care products, such as cosmetics, ointments, medications, emollients, and fragrances.
  • the fibrous articles also may include various powders and particulates to improve absorbency or as delivery vehicles. Examples of powders and particulates include, but are not limited to, talc, starches, various water absorbent, water-dispersible, or water swellable polymers, such as super absorbent polymers, sulfopolyesters, and poly(vinylalcohols), silica, pigments, and microcapsules. Additives may also be present, but are not required, as needed for specific applications.
  • additives include, but are not limited to, oxidative stabilizers, UV absorbers, colorants, pigments, opacifiers (delustrants), optical brighteners, fillers, nucleating agents, plasticizers, viscosity modifiers, surface modifiers, antimicrobials, disinfectants, cold flow inhibitors, branching agents, and catalysts.
  • the fibrous articles described above may be flushable.
  • flushable means capable of being flushed in a conventional toilet, and being introduced into a municipal sewage or residential septic system, without causing an obstruction or blockage in the toilet or sewage system.
  • the fibrous article may further comprise a water-dispersible film comprising a second water-dispersible polymer.
  • the second water-dispersible polymer may be the same as or different from the previously described water-dispersible polymers used in the fibers and fibrous articles of the present invention.
  • the second water-dispersible polymer may be an additional sulfopolyester which, in turn, comprises:
  • n is an integer in the range of 2 to about 500;
  • the additional sulfopolyester may be blended with one or more supplemental polymers, as described hereinabove, to modify the properties of the resulting fibrous article.
  • the supplemental polymer may or may not be water-dispersible depending on the application.
  • the supplemental polymer may be miscible or immiscible with the additional sulfopolyester.
  • the additional sulfopolyester may contain other concentrations of isophthalic acid residues, for example, about 60 to about 95 mole%, and about 75 to about 95 mole%. Further examples of isophthalic acid residue concentrations ranges are about 70 to about 85 mole%, about 85 to about 95 mole% and about 90 to about 95 mole%.
  • the additional sulfopolyester also may comprise about 25 to about 95 mole% of the residues of diethylene glycol. Further examples of diethylene glycol residue concentration ranges include about 50 to about 95 mole%, about 70 to about 95 mole%, and about 75 to about 95 mole%.
  • the additional sulfopolyester also may include the residues of ethylene glycol and/or 1,4-cyclohexanedimethanol. Typical concentration ranges of CHDM residues are about 10 to about 75 mole%, about 25 to about 65 mole%, and about 40 to about 60 mole%. Typical concentration ranges of ethylene glycol residues are about 10 to about 75 mole%, about 25 to about 65 mole%, and about 40 to about 60 mole%. In another embodiment, the additional sulfopolyester comprises is about 75 to about 96 mole% of the residues of isophthalic acid and about 25 to about 95 mole% of the residues of diethylene glycol.
  • the sulfopolyester film component of the fibrous article may be produced as a monolayer or multilayer film.
  • the monolayer film may be produced by conventional casting techniques.
  • the multilayered films may be produced by conventional lamination methods or the like.
  • the film may be of any convenient thickness, but total thickness will normally be between about 2 and about 50 mil.
  • the film-containing fibrous articles may include one or more layers of water- dispersible fibers as described above.
  • the fiber layers may be one or more nonwoven fabric layers, a layer of loosely bound overlapping fibers, or a combination thereof.
  • the film-containing fibrous articles may include personal and health care products as described hereinabove.
  • the fibrous articles also may include various powders and particulates to improve absorbency or as delivery vehicles.
  • our fibrous article comprises a powder comprising a third water- dispersible polymer that may be the same as or different from the water-dispersible polymer components described previously herein.
  • powders and particulates include, but are not limited to, talc, starches, various water absorbent, water-dispersible, or water swellable polymers, such as poly(acrylonitiles), sulfopolyesters, and poly(vinyl alcohols), silica, pigments, and microcapsules.
  • One novel application involves the melt blowing a film or nonwoven fabric onto flat, curved, or shaped surfaces to provide a protective layer.
  • One such layer might provide surface protection to durable equipment during shipping.
  • the outer layers of sulfopolyester could be washed off.
  • a further embodiment of this general application concept could involve articles of personal protection to provide temporary barrier layers for some reusable or limited use garments or coverings.
  • activated carbon and chemical absorbers could be sprayed onto the attenuating filament pattern just prior to the collector to allow the melt blown matrix to anchor these entities on the exposed surface. The chemical absorbers can even be changed in the forward operations area as the threat evolves by melt blowing on another layer.
  • a major advantage inherent to sulfopolyesters is the facile ability to remove or recover the polymer from aqueous dispersions via flocculation or precipitation by adding ionic moieties (i.e., salts). Other methods, such as pH adjustment, adding nonsolvents, freezing, and so forth may also be employed. Therefore, fibrous articles, such as outer wear protective garments, after successful protective barrier use and even if the polymer is rendered as hazardous waste, can potentially be handled safely at much lower volumes for disposal using accepted protocols, such as incineration.
  • Undissolved or dried sulfopolyesters are known to form strong adhesive bonds to a wide array of substrates, including, but not limited to fluff pulp, cotton, acrylics, rayon, lyocell, PLA (polylactides), cellulose acetate, cellulose acetate propionate, poly(ethylene) terephthalate, poly(butylene) terephthalate, poly(trimethylene) terephthalate, poly(cyclohexylene) terephthalate, copolyesters, polyamides (nylons), stainless steel, aluminum, treated polyolefins, PAN (polyacrylonitriles), and polycarbonates.
  • substrates including, but not limited to fluff pulp, cotton, acrylics, rayon, lyocell, PLA (polylactides), cellulose acetate, cellulose acetate propionate, poly(ethylene) terephthalate, poly(butylene) terephthalate, poly(trimethylene) terephthalate, poly(cyclo
  • our nonwoven fabrics may be used as laminating adhesives or binders that may be bonded by known techniques, such as thermal, radio frequency (RF), microwave, and ultrasonic methods. Adaptation of sulfopoly esters to enable RF activation is disclosed in a number of recent patents.
  • our novel nonwoven fabrics may have dual or even multifunctionality in addition to adhesive properties. For example, a disposable baby diaper could be obtained where a nonwoven of the present invention serves as both an water-responsive adhesive as well as a fluid managing component of the final assembly.
  • Our invention also provides a process for water-dispersible fibers comprising: (A) heating a water-dispersible polymer composition to a temperature above its flow point, wherein the polymer composition comprises:
  • n is an integer in the range/of 2 to about 500; (iv) 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof; wherein the polymer composition contains less than 10 weight percent of a pigment or filler, based on the total weight of the polymer composition; and (II) melt spinning filaments.
  • a water-dispersible polymer optionally, may be blended with the sulfopolyester.
  • a water non-dispersible polymer may be blended with the sulfopolyester to form a blend such that blend is an immiscible blend.
  • flow point means the temperature at which the viscosity of the polymer composition permits extrusion or other forms of processing through a spinneret or extrusion die.
  • the dicarboxylic acid residue may comprise from about 60 to about 100 mole% of the acid residues depending on the type and concentration of the sulfomonomer. Other examples of concentration ranges of dicarboxylic acid residues are from about 60 mole% to about 95 mole% and about 70 mole% to about 95 mole%.
  • the preferred dicarboxylic acid residues are isophthalic, terephthalic, and 1 ,4-cyclohexane- dicarboxylic acids or if diesters are used, dimethyl terephthalate, dimethyl isophthalate, and dimethyl- 1 ,4-cyclohexanedicarboxylate with the residues of isophthalic and terephthalic acid being especially preferred.
  • the sulfomonomer may be a dicarboxylic acid or ester thereof containing a sulfonate group, a diol containing a sulfonate group, or a hydroxy acid containing a sulfonate group. Additional examples of concentration ranges for the sulfomonomer residues are about 4 to about 25 mole%, about 4 to about 20 mole%, about 4 to about 15 mole%, and about 4 to about 10 mole%, based on the total repeating units.
  • the cation of the sulfonate salt may be a metal ion such as Li + , Na + , K + , Mg +"1" , Ca + ⁇ Ni "1"1” , Fe + *, and the like.
  • the cation of the sulfonate salt may be non-metallic such as a nitrogenous base as described previously.
  • sulfomonomer residues which may be used in the process of the present invention are the metal sulfonate salt of sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalic acid, or combinations thereof.
  • sulfomonomer which may be used is 5- sodiosulfoisophthalic acid or esters thereof. If the sulfomonomer residue is from 5- sodiosulfoisophthalic acid, typical sulfomonomer concentration ranges are about 4 to about 35 mole%, about 8 to about 30 mole %, and about 10 to 25 mole %, based on the total acid residues.
  • the sulfopolyester of our includes one or more diol residues which may include aliphatic, cycloaliphatic, and aralkyl glycols.
  • the cycloaliphatic diols for example, 1,3- and 1,4-cyclohexanedimethanol, may be present as their pure cis or trans isomers or as a mixture of cis and trans isomers.
  • Non-limiting examples of lower molecular weight polyethylene glycols, e.g., wherein n is from 2 to 6, are diethylene glycol, triethylene glycol, and tetraethylene glycol. Of these lower molecular weight glycols, diethylene and triethylene glycol are most preferred.
  • the sulfopolyester may optionally include a branching monomer.
  • branching monomers are as described hereinabove. Further examples of branching monomer concentration ranges are from 0 to about 20 mole% and from 0 to about 10 mole%.
  • the sulfopolyester of our novel process has a Tg of at least 25 0 C. Further examples of glass transition temperatures exhibited by the sulfopolyester are at least 3O 0 C, at least 35 0 C, at least 4O 0 C, at least 5O 0 C, at least 6O 0 C, at least 65 0 C, at least 8O 0 C, and at least 9O 0 C.
  • typical glass transition temperatures of the dry sulfopolyesters our invention are about 30 0 C, about 48 0 C, about 55 0 C, about 65 0 C, about 7O 0 C, about 75 0 C, about 85 0 C, and about 9O 0 C.
  • the water-dispersible fibers are prepared by a melt blowing process.
  • the polymer is melted in an extruder and forced through a die.
  • the extrudate exiting the die is rapidly attenuated to ultrafine diameters by hot, high velocity air.
  • the orientation, rate of cooling, glass transition temperature (T g ), and rate of crystallization of the fiber are important because they affect the viscosity and processing properties of the polymer during attenuation.
  • the filament is collected on a renewable surface, such as a moving belt, cylindrical drum, rotating mandrel, and so forth.
  • Predrying of pellets are all factors that influence product characteristics such as filament diameters, basis weight, web thickness, pore size, softness, and shrinkage.
  • the high velocity air also may be used to move the filaments in a somewhat random fashion that results in extensive interlacing. If a moving belt is passed under the die, a nonwoven fabric can be produced by a combination of overlapping laydown, mechanical cohesiveness, and thermal bonding of the filaments. Overblowing onto another substrate, such as a spunbond or backing layer, is also possible. If the filaments are taken up on an rotating mandrel, a cylindrical product is formed. A water-dispersible fiber lay-down can also be prepared by the spunbond process.
  • the instant invention therefore, further provides a process for water-dispersible, nonwoven fabric comprising: (A) heating a water-dispersible polymer composition to a temperature above its flow point, wherein the polymer composition comprises:
  • n is an integer in the range of 2 to about 500;
  • a water-dispersible polymer may be blended with the sulfopolyester.
  • a water non-dispersible polymer optionally, may be blended with the sulfopolyester to form a blend such that blend is an immiscible blend.
  • the dicarboxylic acid, sulfomonomer, and branching monomer residues are as described previously.
  • the sulfopolyester has a Tg of at least 25 0 C.
  • glass transition temperatures exhibited by the sulfopolyester are at least 3O 0 C, at least 35 0 C, at least 4O 0 C, at least 5O 0 C, at least 6O 0 C, at least 65 0 C, at least 8O 0 C, and at least 9O 0 C.
  • typical glass transition temperatures of the dry sulfopolyesters our invention are about 3O 0 C, about 48 0 C, about 55 0 C, about 65 0 C, about 7O 0 C, about 75 0 C, about 85 0 C, and about 9O 0 C.
  • the invention is further illustrated by the following examples. EXAMPLES
  • Example 1 All pellet samples were predried under vacuum at room temperature for at least 12 hours.
  • the dispersion times shown in Table 3 are for either complete dispersion or dissolution of the non woven fabric samples.
  • the abbreviation "CE”, used in Tables 2 and 3 mean "comparative example”.
  • a sulfopolyester containing 76 mole%, isophthalic acid, 24 mole% of sodio- sulfoisophthalic acid, 76 mole% diethylene glycol, and 24 mole% 1 ,4-cyclohexane- dimethanol with an Ih. V. of 0.29 and a Tg of 48 0 C was meltblown through a nominal 6-inch die (30 holes/inch in the nosepiece) onto a cylindrical collector using the conditions shown in Table 1. Interleafing paper was not required. A soft, handleable, flexible web was obtained that did not block during the roll winding operation. Physical properties are provided in Table 2. A small piece (I" x 3") of the nonwoven fabric was easily dispersed in both room temperature (RT) and 5O 0 C water with slight agitation as shown by data in Table 3.
  • a sulfopolyester containing 89 mole%, isophthalic acid, 1 1 mole% of sodiosulfoisophthalic acid, 72 mole% diethylene glycol, and 28 mole% ethylene glycol with an Ih.V. of 0.4 and a Tg of 35 0 C was meltblown through a 6-inch die using conditions similar to those in Table 1.
  • a soft, handleable, flexible web was obtained that did not block during a roll winding operation. Physical properties are provided in Table 2.
  • a small piece (I" x 2") of the nonwoven fabric was easily and completely dispersed at 50 0 C and 80 0 C; at RT (23 0 C), the fabric required a longer period of time for complete dispersion as shown by the data in Table 3.
  • compositions in Examples 1 and 2 can be overblown onto other nonwoven substrates. It is also possible to condense and wrap shaped or contoured forms that are used instead of conventional web collectors. Thus, it is possible to obtain circular "roving" or plug forms of the webs.
  • Pellets of a sulfopolyester containing 89 mole%, isophthalic acid, 1 1 mole% of sodiosulfoisophthalic acid, 72 mole% diethylene glycol, and 28 mole% ethylene glycol with an Ih.V. of 0.4 and a Tg of 35 0 C were combined with polypropylene (Basell PF 008) pellets in bicomponent ratios (by wt%) of :
  • the PP had a MFR (melt flow rate) of 800.
  • a melt blowing operation was performed on a line equipped with a 24-inch wide die to yield handleable, soft, flexible, but nonblocking webs with the physical properties provided in Table 2.
  • Small pieces (I" x 4") of nonwoven fabric readily disintegrated as reported in Table 3. None of the fibers, however, were completely water-dispersible because of the insoluble polypropylene component.
  • a circular piece (4" diameter) of the nonwoven produced in Example 2 was used as an adhesive layer between two sheets of cotton fabric.
  • a Hannifin melt press was used to fuse the two sheets of cotton together by applying a pressure 35 psig at 200 0 C for 30 seconds.
  • the resultant assembly exhibited exceptionally strong bond strength.
  • the cotton substrate shredded before adhesive or bond failure. Similar results have also been obtained with other cellulosics and with PET polyester substrates. Strong bonds were also produced by ultrasonic bonding techniques.
  • a PP (Exxon 3356G) with a 1200 MFR was melt blown using a 24" die to yield a flexible nonwoven fabric that did not block and was easily unwound from a roll. Small pieces (I" x 4") did not show any response (i.e., no disintegration or loss in basis weight) to water when immersed in water at RT or 50 0 C for 15 minutes.
  • Unicomponent fibers of a sulfopolyester containing 82 mole% isophthalic acid, 18 mole% of sodiosulfoisophthalic acid, 54 mole% diethylene glycol, and 46 mole% 1 ,4-cyclohexanedimethanol with a Tg of 55 0 C were melt spun at melt temperatures of 245 0 C (473 F) on a lab staple spinning line. As-spun denier was approximately 8 d/f. Some blocking was encountered on the take-up tubes, but the 10-filament strand readily dissolved within 10 - 19 seconds in unagitated, demineralized water at 82 0 C and a pH between 5 and 6.
  • the blend has a Tg of 57 0 C as calculated by taking a weighted average of the Tg's of the component sulfopolyesters.
  • the 10-filament strands did not show any blocking on the take-up tubes, but readily dissolved within 20 — 43 seconds in unagitated, demineralized water at 82° C and a pH between 5 and 6.
  • Example 5 The blend described in Example 5 was co-spun with PET to yield bicomponent islands-in-the-sea fibers.
  • a configuration was obtained where the sulfopolyester “sea” is 20 wt% of the fiber containing 80 wt% of PET "islands".
  • the spun yarn elongation was 190% immediately after spinning. Blocking was not encountered as the yarn was satisfactorily unwound from the bobbins and processed a week after spinning.
  • the "sea” was dissolved by passing the yarn through an 88 0 C soft water bath leaving only fine PET filaments.
  • This prophetic example illustrates the possible application of the multicomponent and microdenier fibers of the present invention to the preparation of specialty papers.
  • the blend described in Example 5 is co-spun with PET to yield bicomponent islands-in-the-sea fibers.
  • the fiber contains approximately 35 wt% sulfopolyester "sea” component and approximately 65 wt% of PET "islands".
  • the uncrimped fiber is cut to 1/8 inch lengths.
  • these short-cut bicomponent fibers are added to the refining operation.
  • the sulfopolyester "sea” is removed in the agitated, aqueous slurry thereby releasing the microdenier PET fibers into the mix.
  • the microdenier PET fibers (“islands") are more effective to increase paper tensile strength than the addition of coarse PET fibers.
  • Bicomponent fibers were made having a 108 islands in the sea structure on a spunbond line using a 24" wide bicomponent spinneret die from Hills Inc., Melbourne, FL, having a total of 2222 die holes in the die plate.
  • Two extruders were connected to melt pumps which were in turn connected to the inlets for both components in the fiber spin die.
  • the primary extruder (A) was connected to the inlet which metered a flow of Eastman F61HC PET polyester to form the island domains in the islands in the sea fiber cross-section structure.
  • the extrusion zones were set to melt the PET entering the die at a temperature of 285°C.
  • the secondary extruder (B) processed Eastman AQ 55 S sulfopolyester polymer from Eastman Chemical Company, Kingsport, TN having an inherent viscosity of about 0.35 and a melt viscosity of about 15,000 poise, measured at 240°C and 1 rad/sec sheer rate and 9,700 poise measured at 240°C and 100 rad/sec sheer rate in a Rheometric Dynamic Analyzer RDAII (Rheometrics Inc. Piscataway, New Jersey) rheometer. Prior to performing a melt viscosity measurement, the sample was dried for two days in a vacuum oven at 60 0 C. The viscosity test was performed using a 25 mm diameter parallel-plate geometry at lmm gap setting.
  • a dynamic frequency sweep was run at a strain rate range of 1 to 400 rad/sec and 10% strain amplitude. Then, the viscosity was measured at 240° C and strain rate of 1 rad/sec. This procedure was followed in determining the viscosity of the sulfopolyester materials used in the subsequent examples.
  • the secondary extruder was set to melt and feed the AQ 55S polymer at a melt temperature of 255°C to the spinnerette die.
  • the two polymers were formed into bicomponent extrudates by extrusion at a throughput rate of 0.6 g/hole/min.
  • the volume ratio of PET to AQ 55S in the bicomponent extrudates was adjusted to yield 60/40 and 70/30 ratios.
  • An aspirator device was used to melt draw the bicomponent extrudates to produce the bicomponent fibers.
  • the flow of air through the aspirator chamber pulled the resultant fibers down.
  • the amount of air flowing downward through the aspirator assembly was controlled by the pressure of the air entering the aspirator.
  • the maximum pressure of the air used in the aspirator to melt draw the bicomponent extrudates was 25 psi. Above this value, the airflow through the aspirator caused the extrudates to break during this melt draw spinning process as the melt draw rate imposed on the bicomponent extrudates was greater than the inherent ductility of the bicomponent extrudates.
  • the bicomponent fibers were laid down into a non-woven web having a fabric weight of 95 grams per square meter (gsm). Evaluation of the bicomponent fibers in this nonwoven web by optical microscopy showed that the PET was present as islands in the center of the fiber structure, but the PET islands around the outer periphery of the bicomponent fiber nearly coalesced together to form a nearly continuous ring of PET polymer around the circumference of the fibers which is not desireable. Microscopy found that the diameter of the bicomponent fibers in the nonwoven web was generally between 15-19 microns, corresponding to an average fiber as-spun denier of about 2.5 denier per filament (dpf). This represents a melt drawn fiber speed of about 2160 meters per minute. As- spun denier is defined as the denier of the fiber (weight in grams of 9000 meters length of fiber) obtained by the melt extrusion and melt drawing steps. The variation in bicomponent fiber diameter indicated non-uniformity in spun-drawing of the fibers.
  • the non-woven web samples were conditioned in a forced-air oven for five minutes at 120°C.
  • the heat treated web exhibited significant shrinkage with the area of the nonwoven web being decreased to only about 12% of the initial area of the web before heating.
  • the bicomponent extrudates could not be melt drawn to the degree required to cause strain induced crystallization of the PET segments in the fibers.
  • the AQ 55S sulfopolyester having this specific inherent viscosity and melt viscosity was not acceptable as the bicomponent extrudates could not be uniformly melt drawn to the desired fine denier.
  • a sulfopolyester polymer with the same chemical composition as commercial Eastman AQ55S polymer was produced, however, the molecular weight was controlled to a lower value characterized by an inherent viscosity of about 0.25.
  • the melt viscosity of this polymer was 3300 poise measured at 240°C and 1 rad/sec shear rate.
  • Bicomponent extrudates having a 16-segment segmented pie structure were made using a bicomponent spinneret die from Hills Inc., Melbourne, FL, having a total of 2222 die holes in the 24 inch wide die plate on a spunbond equipment. Two extruders were used to melt and feed two polymers to this spinnerette die.
  • the primary extruder (A) was connected to the inlet which fed Eastman F61HC PET polyester melt to form the domains or segment slices in the segmented pie cross- section structure.
  • the extrusion zones were set to melt the PET entering the spinnerette die at a temperature of 285°C.
  • the secondary extruder (B) melted and fed the sulfopolyester polymer of Example 8.
  • the secondary extruder was set to extrude the sulfopolyester polymer at a melt temperature of 255°C into the spinnerette die. Except for the spinnerette die used and melt viscosity of the sulfopolyester polymer, the procedure employed in this example was the same as in Comparative Example 8. The melt throughput per hole was 0.6 gm/min. The volume ratio of PET to sulfopolyester in the bicomponent extrudates was set at 70/30 which represents a weight ratio of about 70/30.
  • the bicomponent extrudates were melt drawn using the same aspirator used in Comparative Example 8 to produce the bicomponent fibers. Initially, the input air to the aspirator was set to 25 psi and the fibers had as-spun denier of about 2.0 with the bicomponent fibers exhibiting a uniform diameter profile of about 14-15 microns. The air to the aspirator was increased to a maximum available pressure of 45 psi without breaking the melt extrudates during melt drawing. Using 45 psi air, the bicomponent extrudates were melt drawn down to a fiber as-spun denier of about 1.2 with the bicomponent fibers exhibiting a diameter of 1 1-12 microns when viewed under a microscope.
  • the speed during the melt draw process was calculated to be about 4500 m/min. Although not intending to be bound by theory, at melt draw rates approaching this speed, it is believed that strain induced crystallization of the PET during the melt drawing process begins to occur. As noted above, it is desirable to form some oriented crystallinity in the PET fiber segments during the fiber melt draw process so that the nonwoven web will be more dimensionally stable during subsequent processing.
  • the bicomponent fibers using 45 psi aspirator air pressure were laid down into a nonwoven web with a weight of 140 grams per square meter (gsm).
  • the shrinkage of the nonwoven web was measured by conditioning the material in a forced-air oven for five minutes at 120°C. This example represents a significant reduction in shrinkage compared to the fibers and fabric of Comparative Example 8.
  • This nonwoven web having 140 gsm fabric weight was soaked for five minutes in a static deionized water bath at various temperatures.
  • the soaked nonwoven web was dried, and the percent weight loss due to soaking in deionized water at the various temperatures was measured as shown in Table 4.
  • the sulfopolyester dissipated very readily into deionized water at a temperature of about 25°C. Removal of the sulfopolyester from the bicomponent fibers in the nonwoven web is indicated by the % weight loss. Extensive or complete removal of the sulfopolyester from the bicomponent fibers were observed at temperatures at or above 33°C. If hydroentanglement is used to produce a nonwoven web of these bicomponent fibers comprising the present sulfopolyester polymer of Example 8, it would be expected that the sulfopolyester polymer would be extensively or completely removed by the hydroentangling water jets if the water temperature was above ambient. If it is desired that very little sulfopolyester polymer be removed from these bicomponent fibers during the hydroentanglement step, low water temperature, less than about 25°C , should be used.
  • a sulfopolyester polymer was prepared with the following diacid and diol composition: diacid composition (71 mol % terephthalic acid, 20 mol % isophthalic acid, and 9 mol % 5-(sodiosulfo) isophthalic acid) and diol composition (60 mol % ethylene glycol and 40 mol % diethylene glycol).
  • the sulfopolyester was prepared by high temperature polyesterification under vacuum. The esterification conditions were controlled to produce a sulfopolyester having an inherent viscosity of about 0.31. The melt viscosity of this sulfopolyester was measured to be in the range of about 3000- 4000 poise at 240°C and 1 rad/sec shear rate.
  • the sulfopolyester polymer of Example 10 was spun into bicomponent segmented pie fibers and nonwoven web according to the same procedure described in Example 9.
  • the primary extruder (A) fed Eastman F61HC PET polyester melt to form the larger segment slices in the segmented pie structure.
  • the extrusion zones were set to melt the PET entering the spinnerette die at a temperature of 285°C.
  • the secondary extruder (B) processed the sulfopolyester polymer of Example 10 which was fed at a melt temperature of 255°C into the spinnerette die.
  • the melt throughput rate per hole was 0.6 gm/min.
  • the volume ratio of PET to sulfopolyester in the bicomponent extrudates was set at 70/30 which represents the weight ratio of about 70/30.
  • the cross-section of the bicomponent extrudates had wedge shaped domains of PET with sulfopolyester polymer separating these domains.
  • the bicomponent extrudates were melt drawn using the same aspirator assembly used in Comparative Example 8 to produce the bicomponent fiber.
  • the maximum available pressure of the air to the aspirator without breaking the bicomponent fibers during drawing was 45 psi.
  • the bicomponent extrudates were melt drawn down to bicomponent fibers with as-spun denier of about 1.2 with the bicomponent fibers exhibiting a diameter of about 11-12 microns when viewed under a microscope.
  • the speed during the melt drawing process was calculated to be about 4500 m/min.
  • the bicomponent fibers were laid down into nonwoven webs having weights of 140 gsm and 110 gsm.
  • the shrinkage of the webs was measured by conditioning the material in a forced-air oven for five minutes at 120°C.
  • the area of the nonwoven webs after shrinkage was about 29% of the webs' starting areas.
  • the nonwoven web having 110 gsm fabric weight, was soaked for eight minutes in a static deionized water bath at various temperatures. The soaked nonwoven web was dried and the percent weight loss due to soaking in deionized water at the various temperatures was measured as shown in Table 5.
  • the sulfopolyester polymer dissipated very readily into deionized water at temperatures above about 46°C, with the removal of the sulfopolyester polymer from the fibers being very extensive or complete at temperatures above 51 °C as shown by the weight loss.
  • a weight loss of about 30% represented complete removal of the sulfopolyester from the bicomponent fibers in the nonwoven web. If hydroentanglement is used to process this non- woven web of bicomponent fibers comprising this sulfopolyester, it would be expected that the polymer would not be extensively removed by the hydroentangling water jets at water temperatures below 40°C.
  • Example 12 The nonwoven webs of Example 1 1 having basis weights of both 140 gsm and 110 gsm were hydroentangled using a hydroentangling apparatus manufactured by Fleissner, GmbH, Egelsbach, Germany. The machine had five total hydroentangling stations wherein three sets of jets contacted the top side of the nonwoven web and two sets of jets contacted the opposite side of the nonwoven web.
  • the water jets comprised a series of fine orifices about 100 microns in diameter machined in two- feet wide jet strips. The water pressure to the jets was set at 60 bar (Jet Strip # 1), 190 bar (Jet Strips # 2 and 3), and 230 bar (Jet Strips # 4 and 5).
  • the temperature of the water to the jets was found to be in the range of about 40-45°C.
  • the nonwoven fabric exiting the hydroentangling unit was strongly tied together.
  • the continuous fibers were knotted together to produce a hydroentangled nonwoven fabric with high resistance to tearing when stretched in both directions.
  • the hydroentangled nonwoven fabric was fastened onto a tenter frame comprising a rigid rectangular frame with a series of pins around the periphery thereof.
  • the fabric was fastened to the pins to restrain the fabric from shrinking as it was heated.
  • the frame with the fabric sample was placed in a forced-air oven for three minutes at 130°C to cause the fabric to heat set while being restrained.
  • the conditioned fabric was cut into a sample specimen of measured size, and the specimen was conditioned at 130°C without restraint by a tenter frame.
  • the dimensions of the hydroentangled nonwoven fabric after this conditioning were measured and only minimal shrinkage ( ⁇ 0.5% reduction in dimension) was observed. It was apparent that heat setting of the hydroentangled nonwoven fabric was sufficient to produce a dimensionally stable nonwoven fabric.
  • the hydroentangled nonwoven fabric after being heat set as described above, was washed in 90°C deionized water to remove the sulfopolyester polymer and leave the PET monocomponent fiber segments remaining in the hydroentangled fabric. After repeated washings, the dried fabric exhibited a weight loss of approximately 26 %. Washing the nonwoven web before hydroentangling demonstrated a weight loss of 31.3 %. Therefore, the hydroentangling process removed some of the sulfopolyester from the nonwoven web, but this amount was relatively small. In order to lessen the amount of sulfopolyester removed during hydroentanglement, the water temperature of the hydroentanglement jets should be lowered to below 40°C.
  • the sulfopolyester of Example 10 was found to give segmented pie fibers having good segment distribution where the water non-dispersable polymer segments formed individual fibers of similar size and shape after removal of the sulfopolyester polymer.
  • the rheology of the sulfopolyester was suitable to allow the bicomponent extrudates to be melt drawn at high rates to achieve fine denier bicomponent fibers with as-spun denier as low as about 1.0. These bicomponent fibers are capable of being laid down into a non-woven web which could be hydroentangled without experiencing significant loss of sulfopolyester polymer to produce the nonwoven fabric.
  • the nonwoven fabric produced by hydroentangling the non- woven web exhibited high strength and could be heat set at temperatures of about 120°C or higher to produce nonwoven fabric with excellent dimensional stability.
  • the sulfopolyester polymer was removed from the hydroentangled nonwoven fabric in a washing step. This resulted in a strong nonwoven fabric product with lighter fabric weight and much greater flexibility and softer hand.
  • the monocomponent PET fibers in this nonwoven fabric product were wedge shaped and exhibited an average denier of about 0.1.
  • a sulfopolyester polymer was prepared with the following diacid and diol composition: diacid composition (69 mol % terephthalic acid, 22.5 mol % isophthalic acid, and 8.5 mol % 5-(sodiosulfo) isophthalic acid) and diol composition (65 mol % ethylene glycol and 35 mol % diethylene glycol).
  • the sulfopolyester was prepared by high temperature polyesterif ⁇ cation under vacuum. The esterification conditions were controlled to produce a sulfopolyester having an inherent viscosity of about 0.33. The melt viscosity of this sulfopolyester was measured to be in the range of about 3000- 4000 poise at 240°C and 1 rad/sec shear rate.
  • Example 14 The sulfopolyester polymer of Example 13 was spun into bicomponent islands-in-sea cross-section configuration with 16 islands on a spunbond line.
  • the extrusion zones were set to melt the PET entering the spinnerette die at a temperature of about 29O 0 C.
  • the secondary extruder (B) processed the sulfopolyester polymer of Example 13 which was fed at a melt temperature of about 260°C into the spinnerette die.
  • the volume ratio of PET to sulfopolyester in the bicomponent extrudates was set at 70/30 which represents the weight ratio of about 70/30.
  • the melt throughput rate through the spinneret was 0.6 g/hole/minute.
  • the cross-section of the bicomponent extrudates had round shaped island domains of PET with sulfopolyester polymer
  • the bicomponent extrudates were melt drawn using an aspirator assembly.
  • the maximum available pressure of the air to the aspirator without breaking the bicomponent fibers during melt drawing was 50 psi.
  • the bicomponent extrudates were melt drawn down to bicomponent fibers with as-spun denier of about 1.4 with the bicomponent fibers exhibiting a diameter of about 12 microns when viewed under a microscope.
  • the speed during the drawing process was calculated to be about 3900 m/min.
  • the sulfopolyester polymer of Example 13 was spun into bicomponent islands- in-the- sea cross-section fibers with 64 islands fibers using a bicomponent extrusion line.
  • the inherent viscosity of polyester was 0.61 dL/g while the melt viscosity of dry sulfopolyester was about 7000 poise measured at 240°C and 1 rad/sec strain rate using the melt viscosity measurement procedure described earlier.
  • These islands-in-sea bicomponent fibers were made using a spinneret with 198 holes and a throughput rate of 0.85 gms/minute/hole.
  • the polymer ratio between "islands" polyester and “sea” sulfopolyester was 65% to 35%.
  • These bicomponent fibers were spun using an extrusion temperature of 280°C for the polyester component and 260°C for the sulfopolyester component.
  • the bicomponent fiber contains a multiplicity of filaments (198 filaments) and was melt spun at a speed of about 530 meters/minute, forming filaments with a nominal denier per filament of about 14.
  • a finish solution of 24 wt% PT 769 finish from Goulston Technologies was applied to the bicomponent fiber using a kiss roll applicator.
  • the filaments of the bicomponent fiber were then drawn in line using a set of two godet rolls, heated to 90°C and 130 0 C respectively, and the final draw roll operating at a speed of about 1750 meters/minute, to provide a filament draw ratio of about 3.3X forming the drawn islands-in-sea bicomponent filaments with a nominal denier per filament of about 4.5 or an average diameter of about 25 microns.
  • These filaments comprised the polyester microfiber "islands" having an average diameter of about 2.5 microns.
  • the drawn islands-in-sea bicomponent fibers of Example 15 were cut into short length fibers of 3.2 millimeters and 6.4 millimeters cut lengths, thereby, producing short length bicomponent fibers with 64 islands-in-sea cross-section configurations.
  • These short cut bicomponent fibers comprised "islands" of polyester and "sea” of water dispersible sulfopolyester polymer.
  • the cross-sectional distribution of islands and sea was essentially consistent along the length of these short cut bicomponent fibers.
  • the drawn islands-in-sea bicomponent fibers of Example 15 were soaked in soft water for about 24 hours and then cut into short length fibers of 3.2 millimeters and 6.4 millimeters cut lengths.
  • the water dispersible sulfopolyester was at least partially emulsified prior to cutting into short length fibers. Partial separation of islands from the sea component was therefore effected, thereby, producing partially emulsified short length islands-in-sea bicomponent fibers.
  • the short cut length islands-in-sea bicomponent fibers of Example 16 were washed using soft water at 80 0 C to remove the water dispersible sulfopolyester "sea” component, thereby, releasing the polyester microfibers which were the "islands" component of the bicomponent fibers.
  • the washed polyester microfibers were rinsed using soft water at 25°C to essentially remove most of the "sea” component.
  • the optical microscopic observation of the washed polyester microfibers showed an average diameter of about 2.5 microns and lengths of 3.2 and 6.4 millimeters.
  • the short cut length partially emulsified islands-in-sea bicomponent fibers of Example 17 were washed using soft water at 80°C to remove the water dispersible sulfopolyester "sea" component, thereby, releasing the polyester microfibers which were the "islands" component of the fibers.
  • the washed polyester microfibers were rinsed using soft water at 25°C to essentially remove most of the "sea” component.
  • the optical microscopic observation of the washed polyester microfibers showed polyester microfibers of average diameter of about 2.5 microns and lengths of 3.2 and 6.4 millimeters. Comparative Example 20
  • Wet-laid hand sheets were prepared using the following procedure. 7.5 gms of Albacel Southern Bleached Softwood Kraft (SBSK) from International Paper, Memphis, Tennessee, U.S.A. and 188 gms of room temperature water were placed in a 1000 ml pulper and pulped for 30 seconds at 7000 rpm to produce a pulped mixture. This pulped mixture was transferred into an 8 liter metal beaker along with 7312 gms of room temperature water to make about 0.1% consistency (7500 gms water and 7.5 gms fibrous material) pulp slurry. This pulp slurry was agitated using a high speed impeller mixer for 60 seconds. Procedure to make the hand sheet from this pulp slurry was as follows.
  • the pulp slurry was poured into a 25 centimeters x 30 centimeters hand sheet mold while continuing to stir.
  • the drop valve was pulled, and the pulp fibers were allowed to drain on a screen to form a hand sheet.
  • 750 grams per square meter (gsm) blotter paper was placed on top of the formed hand sheet, and the blotter paper was flattened onto the hand sheet.
  • the screen frame was raised and inverted onto a clean release paper and allowed to sit for 10 minutes.
  • the screen was raised vertically away from the formed hand sheet.
  • Two two sheets of 750 gsm blotter paper were placed on top of the formed hand sheet.
  • the hand sheet was dried along with the three blotter papers using a Norwood Dryer at about 88°C for 15 minutes.
  • One blotter paper was removed leaving one blotter paper on each side of the hand sheet.
  • the hand sheet was dried using a Williams Dryer at 65°C for 15 minutes.
  • the hand sheet was then further dried for 12 to 24 hours using a 40 kg dry press.
  • the blotter paper was removed to obtain the dry hand sheet sample.
  • the hand sheet was trimmed to 21.6 centimeters by 27.9 centimeters dimensions for testing.
  • Wet-laid hand sheets were prepared using the following procedure. 7.5 gms of Albacel Southern Bleached Softwood Kraft (SBSK) from International Paper, Memphis, Tennessee, U.S.A., 0.3 gms of Solivitose N pre-gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands, and 188 gms of room temperature water were placed in a 1000 ml pulper and pulped for 30 seconds at 7000 rpm to produce a pulped mixture.
  • SBSK Albacel Southern Bleached Softwood Kraft
  • This pulped mixture was transferred into an 8 liter metal beaker along with 7312 gms of room temperature water to make about 0.1% consistency (7500 gms water and 7.5 gms fibrous material) to produce a pulp slurry.
  • This pulp slurry was agitated using a high speed impeller mixer for 60 seconds. The rest of procedure for making hand sheet from this pulp slurry was same as in Example 20.
  • Wet-laid hand sheets were prepared using the following procedure. 6.0 gms of Albacel Southern Bleached Softwood Kraft (SBSK) from International Paper, Memphis, Tennessee, U.S.A., 0.3 gms of Solivitose N pre-gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands, 1.5 gms of 3.2 millimeter cut length islands-in-sea fibers of Example 16, and 188 gms of room temperature water were placed in a 1000 ml pulper and pulped for 30 seconds at 7000 rpm to produce a fiber mix slurry.
  • SBSK Albacel Southern Bleached Softwood Kraft
  • This fiber mix slurry was heated to 82°C for 10 seconds to emulsify and remove the water dispersible sulfopolyester component in the islands-in-sea fibers and release polyester microfibers.
  • the fiber mix slurry was then strained to produce a sulfopolyester dispersion comprising the sulfopolyester and a microfiber-containing mixture comprising pulp fibers and polyester microfiber.
  • the microfiber-containing mixture was further rinsed using 500 gms of room temperature water to further remove the water dispersible sulfopolyester from the microfiber- containing mixture.
  • microfiber-containing mixture was transferred into an 8 liter metal beaker along with 7312 gms of room temperature water to make about 0.1% consistency (7500 gms water and 7.5 gms fibrous material) to produce a microfiber- containing slurry.
  • This microfiber-containing slurry was agitated using a high speed impeller mixer for 60 seconds. The rest of procedure for making hand sheet from this microfiber-containing slurry was same as in Example 20. Comparative Example 23
  • Wet-laid hand sheets were prepared using the following procedure. 7.5 gms of MicroStrand 475-106 micro glass fiber available from Johns Manville, Denver, Colorado, U.S.A., 0.3 gms of Solivitose N pre-gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands, and 188 gms of room temperature water were placed in a 1000 ml pulper and pulped for 30 seconds at 7000 rpm to produce a glass fiber mixture. This glass fiber mixture was transferred into an 8 liter metal beaker along with 7312 gms of room temperature water to make about 0.1% consistency (7500 gms water and 7.5 gms fibrous material) to produce a glass fiber slurry. This glass fiber slurry was agitated using a high speed impeller mixer for 60 seconds. The rest of procedure for making hand sheet from this glass fiber slurry was same as in Example 20.
  • Wet-laid hand sheets were prepared using the following procedure. 3.8 gms of MicroStrand 475-106 micro glass fiber available from Johns Manville, Denver, Colorado, U.S.A., 3.8 gms of 3.2 millimeter cut length islands-in-sea fibers of Example 16, 0.3 gms of Solivitose N pre-gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands, and 188 gms of room temperature water were placed in a 1000 ml pulper and pulped for 30 seconds at 7000 rpm to produce a fiber mix slurry.
  • This fiber mix slurry was heated to 82°C for 10 seconds to emulsify and remove the water dispersible sulfopolyester component in the islands-in-sea bicomponent fibers and release polyester microfibers.
  • the fiber mix slurry was then strained to produce a sulfopolyester dispersion comprising the sulfopolyester and a microfiber-containing mixture comprising glass microfibers and polyester microfiber.
  • the microfiber-containing mixture was further rinsed using 500 gms of room temperature water to further remove the sulfopolyester from the microfiber-containing mixture.
  • This microfiber-containing mixture was transferred into an 8 liter metal beaker along with 7312 gms of room temperature water to make about 0.1% consistency (7500 gms water and 7.5 gms fibrous material) to produce a microfiber- containing slurry.
  • This microf ⁇ ber-containing slurry was agitated using a high speed impeller mixer for 60 seconds. The rest of procedure for making hand sheet from this microfiber-containing slurry was same as in Example 20.
  • Wet-laid hand sheets were prepared using the following procedure. 7.5 gms of 3.2 millimeter cut length islands-in-sea fibers of Example 16, 0.3 gms of Solivitose N pre-gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands, and 188 gms of room temperature water were placed in a 1000 ml pulper and pulped for 30 seconds at 7000 rpm to produce a fiber mix slurry. This fiber mix slurry was heated to 82°C for 10 seconds to emulsify and remove the water dispersible sulfopolyester component in the islands-in-sea fibers and release polyester microfibers.
  • the fiber mix slurry was then strained to produce a sulfopolyester dispersion and polyester microfibers.
  • the sulfopolyester dispersion was comprised of water dispersible sulfopolyester.
  • the polyester microfibers were rinsed using 500 gms of room temperature water to further remove the sulfopolyester from the polyester microfibers.
  • These polyester microfibers were transferred into an 8 liter metal beaker along with 7312 gms of room temperature water to make about 0.1% consistency (7500 gms water and 7.5 gms fibrous material) to produce a microfiber slurry.
  • This microfiber slurry was agitated using a high speed impeller mixer for 60 seconds. The rest of procedure for making hand sheet from this microfiber slurry was same as in Example 20.
  • the hand sheet basis weight was determined by weighing the hand sheet and calculating weight in grams per square meter (gsm).
  • Hand sheet thickness was measured using an Ono Sokki EG-233 thickness gauge and reported as thickness in millimeters. Density was calculated as weight in grams per cubic centimeter.
  • Porosity was measured using a Greiner Porosity Manometer with 1.9 x 1.9 cm square opening head and 100 cc capacity. Porosity is reported as average time in seconds (4 replicates) for 100 cc of water to pass through the sample.
  • Tensile properties were measured using an Instron Model TM for six 30 mm x 105 mm test strips. An average of six measurements is reported for each example. It can be observed from these test data that significant improvement in tensile properties of wet-laid fibrous structures is obtained by the addition of polyester microfibers of the current invention.
  • the sulfopolyester polymer of Example 13 was spun into bicomponent islands-in-the- sea cross-section fibers with 37 islands fibers using a bicomponent extrusion line.
  • the primary extruder fed Eastman F61HC polyester to form the "islands" in the islands-in-the-sea cross-section structure.
  • the secondary extruder fed the water dispersible sulfopolyester polymer to form the "sea" in the islands-in-sea bicomponent fiber.
  • the inherent viscosity of the polyester was 0.61 dL/g while the melt viscosity of dry sulfopolyester was about 7000 poise measured at 240°C and 1 rad/sec strain rate using the melt viscosity measurement procedure described previously.
  • These islands-in-sea bicomponent fibers were made using a spinneret with 72 holes and a throughput rate of 1.15gms/minute/hole.
  • the polymer ratio between "islands" polyester and “sea” sulfopolyester was 2 to 1.
  • These bicomponent fibers were spun using an extrusion temperature of 280°C for the polyester component and 255°C for the water dispersible sulfopolyester component.
  • This bicomponent fiber contained a multiplicity of filaments (198 filaments) and was melt spun at a speed of about 530 meters/minute forming filaments with a nominal denier per filament of 19.5.
  • a finish solution of 24% by weight PT 769 finish from Goulston Technologies was applied to the bicomponent fiber using a kiss roll applicator.
  • the filaments of the bicomponent fiber were then drawn in line using a set of two godet rolls, heated to 95°C and 130°C respectively, and the final draw roll operating at a speed of about 1750 meters/minute, to provide a filament draw ratio of about 3.3X forming the drawn islands-in-sea bicomponent filaments with a nominal denier per filament of about 5.9 or an average diameter of about 29 microns.
  • These filaments comprised the polyester microfiber islands of average diameter of about 3.9 microns.
  • the drawn islands-in-sea bicomponent fibers of Example 26 were cut into short length bicomponent fibers of 3.2 millimeters and 6.4 millimeters cut length, thereby, producing short length fibers with 37 islands-in-sea cross-section configurations.
  • These fibers comprised "islands” of polyester and "sea” of water dispersible sulfopolyester polymers.
  • the cross-sectional distribution of "islands” and "sea” was essentially consistent along the length of these bicomponent fibers.
  • the short cut length islands-in-sea fibers of Example 27 were washed using soft water at 80°C to remove the water dispersible sulfopolyester "sea" component, thereby, releasing the polyester microfibers which were the "islands" component of the bicomponent fibers.
  • the washed polyester microfibers were rinsed using soft water at 25°C to essentially remove most of the "sea” component.
  • the optical microscopic observation of the washed polyester microfibers had an average diameter of about 3.9 microns and lengths of 3.2 and 6.4 millimeters.
  • the sulfopolyester polymer of Example 13 was spun into bicomponent islands-in-the- sea cross-section fibers with 37 islands fibers using a bicomponent extrusion line.
  • the primary extruder fed polyester to form the "islands" in the islands-in-the-sea fiber cross-section structure.
  • the secondary extruder fed the water dispersible sulfopolyester polymer to form the "sea" in the islands-in-sea bicomponent fiber.
  • the inherent viscosity of the polyester was 0.52 dL/g while the melt viscosity of the dry water dispersible sulfopolyester was about 3500 poise measured at 240°C and 1 rad/sec strain rate using the melt viscosity measurement procedure described previously.
  • These islands-in-sea bicomponent fibers were made using two spinnerets with 175 holes each and throughput rate of 1.0 gms/minute/hole.
  • the polymer ratio between "islands" polyester and "sea” sulfopolyester was 70% to 30%.
  • These bicomponent fibers were spun using an extrusion temperature of 280°C for the polyester component and 255°C for the sulfopolyester component.
  • the bicomponent fibers contained a multiplicity of filaments (350 filaments) and were melt spun at a speed of about 1000 meters/minute using a take-up roll heated to 100°C forming filaments with a nominal denier per filament of about 9 and an average fiber diameter of about 36 microns.
  • a finish solution of 24 wt% PT 769 finish was applied to the bicomponent fiber using a kiss roll applicator.
  • the filaments of the bicomponent fiber were combined and were then drawn 3.0x on a draw line at draw roll speed of 100 m/minute and temperature of 38°C forming drawn islands-in-sea bicomponent filaments with an average denier per filament of about 3 and average diameter of about 20 microns.
  • These drawn island-in-sea bicomponent fibers were cut into short length fibers of about 6.4 millimeters length.
  • These short length islands-in-sea bicomponent fibers were comprised of polyester microfiber "islands" of average diameter of about 2.8 microns.
  • Example 29 The short cut length islands-in-sea bicomponent fibers of Example 29 were washed using soft water at 80°C to remove the water dispersible sulfopolyester "sea” component, thereby, releasing the polyester microfibers which were the "islands” component of the fibers.
  • the washed polyester microfibers were rinsed using soft water at 25°C to essentially remove most of the "sea” component.
  • the optical microscopic observation of washed fibers showed polyester microfibers of average diameter of about 2.8 microns and lengths of about 6.4 millimeters.
  • Wet-laid microfiber stock hand sheets were prepared using the following procedure. 56.3 gms of 3.2 millimeter cut length islands-in-sea bicomponent fibers of Example 16, 2.3 gms of Solivitose N pre-gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands, and 1410 gms of room temperature water were placed in a 2 liter beaker to produce a fiber slurry. The fiber slurry was stirred. One quarter amount of this fiber slurry, about 352 ml, was placed in 1000 ml pulper and pulped for 30 seconds at 7000 rpm.
  • This fiber slurry was heated to 82°C for 10 seconds to emulsify and remove the water dispersible sulfopolyester component in the islands-in-sea bicomponent fibers and release polyester microfibers.
  • the fiber slurry was then strained to produce a sulfopolyester dispersion and polyester microfibers.
  • These polyester microfibers were rinsed using 500 gms of room temperature water to further remove the sulfopolyester from the polyester microfibers. Sufficient room temperature water was added to produce 352 ml of microfiber slurry.
  • This microfiber slurry was re-pulped for 30 seconds at 7000 rpm. These microfibers were transferred into an 8 liter metal beaker.
  • the remaining three quarters of the fiber slurry were similarly pulped, washed, rinsed and re-pulped and transferred to the 8 liter metal beaker. 6090 gms of room temperature water was then added to make about 0.49% consistency (7500 gms water and 36.6 gms of polyester microfibers) to produce a microfiber slurry. This microfiber slurry was agitated using a high speed impeller mixer for 60 seconds. The rest of procedure for making hand sheet from this microfiber slurry was same as in Example 20.
  • the microfiber stock hand sheet with the basis weight of about 490 gsm was comprised of polyester microfibers of average diameter of about 2.5 microns and average length of about 3.2 millimeters.
  • Wet-laid hand sheets were prepared using the following procedure. 7.5 gms of polyester microfiber stock hand sheet of Example 31, 0.3 gms of Solivitose N pre- gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands, and 188 gms of room temperature water were placed in a 1000 ml pulper and pulped for 30 seconds at 7000 rpm. The microfibers were transferred into an 8 liter metal beaker along with 7312 gms of room temperature water to make about 0.1% consistency (7500 gms water and 7.5 gms fibrous material) to produce a microfiber slurry. This microfiber slurry was agitated using a high speed impeller mixer for 60 seconds. The rest of procedure for making hand sheet from this slurry was same as in Example 20. A 100 gsm wet-laid hand sheet of polyester microfibers was obtained having an average diameter of about 2.5 microns.
  • the 6.4 millimeter cut length islands-in-sea bicomponent fibers of Example 29 were washed using soft water at 80 0 C to remove the water dispersible sulfopolyester "sea" component, thereby, releasing the polyester microfibers which were the "islands" component of the bicomponent fibers.
  • the washed polyester microfibers were rinsed using soft water at 25°C to essentially remove most of the "sea” component.
  • the optical microscopic observation of the washed polyester microfibers showed an average diameter of about 2.5 microns and lengths of 6.4 millimeters.
  • Example 16 The short cut length islands-in-sea bicomponent fibers of Example 16, Example 27 and Example 29 were washed separately using soft water at 80 0 C containing about 1% by weight based on the weight of the bicomponent fibers of ethylene diamine tetra acetic acid tetra sodium salt (Na 4 EDTA) from Sigma-Aldrich Company, Atlanta, Georgia to remove the water dispersible sulfopolyester "sea" component, thereby, releasing the polyester microfibers which were the "islands" component of the bicomponent fibers.
  • Na 4 EDTA ethylene diamine tetra acetic acid tetra sodium salt
  • the washed polyester microfibers were rinsed using soft water at 25°C to essentially remove most of the "sea" component.
  • the optical microscopic observation of washed polyester microfibers showed excellent release and separation of polyester microfibers.
  • Use of a water softing agent, such as Na 4 EDTA in the water prevents any Ca 4"1" ion exchange on the sulfopolyester which can adversely affect the water dispersiblity of sulfopolyester.
  • Typical soft water may contain up to 15 ppm of Ca +"1" ion concentration. It is desirable that the soft water used in the processes described here should have essentially zero concentration of Ca + * and other multi-valent ions or alternately use sufficient amount of water softening agent, such as Na 4 EDTA, to bind these Ca + * ions and other multi-valent ions.
  • water softening agent such as Na 4 EDTA
  • the short cut length islands-in-sea bicomponent fibers of Example 16 and Example 27 were processed separately using the following procedure. 17 grams of Solivitose N pre-gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands were added to the distilled water. After the starch was fully dissolved or hydrolyzed, then 429 grams of short cut length islands-in-sea bicomponent fibers were slowly added to the distilled water to produce a fiber slurry. A Williams Rotary Continuous Feed Refiner (5 inch diameter) was turned on to refine or mix the fiber slurry in order to provide sufficient shearing action for the water dispersible sulfopolyester to be separated from the polyester microfibers.
  • the contents of the stock chest were poured into a 24 liter stainless steel container, and the lid was secured.
  • the stainless steel container was placed on a propane cooker and heated until the fiber slurry began to boil at about 97°C in order to remove the sulfopolyester component in the island-in-sea fibers and release polyester microfibers. After the fiber slurry reached boiling, it was agitated with a manual agitating paddle.
  • the contents of the stainless steel container were poured into a 27in x 15in x 6 in deep False Bottom Knuche with a 30 mesh screen to produce a sulfopolyester dispersion and polyester microfibers.
  • the sulfopolyester dispersion comprised water and water dispersible sulfopolyester.
  • the polyester microfibers were rinsed in the Knuche for 15 seconds with 10 liters of soft water at 17°C, and squeezed to remove excess water.
  • polyester microfiber dry fiber basis
  • a horse power hydropulper manufactured by Hermann Manufacturing Company for 3 minutes (9,000 revolutions) to make a microfiber slurry of 1% consistency.
  • Handsheets were made using the procedure described previously in Example 20.

Abstract

A water non-dispersible polymer microfiber is provided comprising at least one water non-dispersible polymer wherein the water non-dispersible polymer microfiber has an equivalent diameter of less than 5 microns and length of less than 25 millimeters. A process for producing water non-dispersible polymer microfϊbers is also provided, the process comprising: a) cutting a multicomponent fiber into cut multicomponent fibers; b) contacting a fiber-containing feedstock with water to produce a fiber mix slurry; wherein the fiber-containing feedstock comprises cut multicomponent fibers; c) heating the fiber mix slurry to produce a heated fiber mix slurry; d) optionally, mixing the fiber mix slurry in a shearing zone; e) removing at least a portion of the sulfopolyester from the multicomponent fiber to produce a slurry mixture comprising a sulfopolyester dispersion and water non-dispersible polymer microfibers; and f) separating the water non-dispersible polymer microfibers from the slurry mixture. A process for producing a nonwoven article is also provided.

Description

NONWOVENS PRODUCED FROM MULTICOMPONENT FIBERS
CROSS REFERENCES TO RELATED APPLICATIONS This application is a continuation-in-part application claiming priority to Provisional Application Serial No. 61/041,699, filed April 2, 2008 and continuation- in-part application Application Serial No. 11/648,955 filed January 3rd, 2007, which is a continuation-in-part of Application Serial No. 1 1,344,320 filed January 31st, 2006, which is a continuation-in-part of Application Serial No. 11/204,868, filed August 16, 2005, which is a divisional of Application Serial No. 10/850,548, filed May 20, 2004, now issued as U.S. Patent No. 6,989,193, which is a continuation-in-part of Application Serial No. 10/465,698, filed June 19, 2003. The foregoing applications are hereby incorporated by reference.
FIELD OF THE INVENTION
The present invention pertains to water-dispersible fibers and fibrous articles comprising a sulfopolyester. The invention further pertains to multicomponent fibers comprising a sulfopolyester and the microdenier fibers and fibrous articles prepared therefrom. The invention also pertains to processes for water-dispersible, multicomponent, and microdenier fibers and to nonwoven fabrics prepared therefrom. The fibers and fibrous articles have applications in flushable personal care products and medical products.
BACKGROUND OF THE INVENTION
Fibers, melt blown webs and other melt spun fibrous articles have been made from thermoplastic polymers, such as poly(propylene), polyamides, and polyesters. One common application of these fibers and fibrous articles are nonwoven fabrics and, in particular, in personal care products such as wipes, feminine hygiene products, baby diapers, adult incontinence briefs, hospital/surgical and other medical disposables, protective fabrics and layers, geotextiles, industrial wipes, and filter media. Unfortunately, the personal care products made from conventional thermoplastic polymers are difficult to dispose of and are usually placed in landfills. One promising alternative method of disposal is to make these products or their components "flushable", i.e., compatible with public sewerage systems. The use of water-dispersible or water-soluble materials also improves recyclability and reclamation of personal care products. The various thermoplastic polymers now used in personal care products are not inherently water-dispersible or soluble and, hence, do not produce articles that readily disintegrate and can be disposed of in a sewerage system or recycled easily.
The desirability of flushable personal care products has resulted in a need for fibers, nonwovens, and other fibrous articles with various degrees of water- responsiyity. Various approaches to addressing these needs have been described, for example, in U.S. Patent No.'s 6,548,592; 6,552,162; 5,281,306; 5,292,581; 5,935,880; and 5,509,913; U.S. Patent Application Serial No.'s 09/775,312; and 09/752,017; and PCT International Publication No. WO 01/66666 A2. These approaches, however, suffer from a number of disadvantages and do not provide a fibrous article, such as a fiber or nonwoven fabric, that possesses a satisfactory balance of performance properties, such as tensile strength, absorptivity, flexibility, and fabric integrity under both wet or dry conditions.
For example, typical nonwoven technology is based on the multidirectional deposition of fibers that are treated with a resin binding adhesive to form a web having strong integrity and other desirable properties. The resulting assemblies, however, generally have poor water-responsivity and are not suitable for flushable applications. The presence of binder also may result in undesirable properties in the final product, such as reduced sheet wettability, increased stiffness, stickiness, and higher production costs. It is also difficult to produce a binder that will exhibit adequate wet strength during use and yet disperse quickly upon disposal. Thus, nonwoven assemblies using these binders may either disintegrate slowly under ambient conditions or have less than adequate wet strength properties in the presence of body fluids. To address this problem, pH and ion-sensitive water-dispersible binders, such as lattices containing acrylic or methacrylic acid with or without added salts, are known and described, for example, in U.S. Patent No. 6,548,592 Bl . Ion concentrations and pH levels in public sewerage and residential septic systems, however, can vary widely among geographical locations and may not be sufficient for the binder to become soluble and disperse. In this case, the fibrous articles will not disintegrate after disposal and can clog drains or sewer laterals.
Multicomponent fibers containing a water-dispersible component and a thermoplastic water non-dispersible component have been described, for example, in U.S. Patent No.'s 5,916,678; 5,405,698; 4,966,808; 5,525282; 5,366,804; 5,486,418. For example, these multicomponent fibers may be a bicomponent fiber having a shaped or engineered transverse cross section such as, for example, an islands-in-the- sea, sheath core, side-by-side, or segmented pie configuration. The multicomponent fiber can be subjected to water or a dilute alkaline solution where the water- dispersible component is dissolved away to leave the water non-dispersible component behind as separate, independent fibers of extremely small fineness. Polymers which have good water dispersibility, however, often impart tackiness to the resulting multicomponent fibers, which causes the fiber to stick together, block, or fuse during winding or storage after several days, especially under hot, humid conditions. To prevent fusing, often a fatty acid or oil-based finish is applied to the surface of the fiber. In addition, large proportions of pigments or fillers are sometimes added to water dispersible polymers to prevent fusing of the fibers as described, for example, in U.S. Patent No. 6,171,685. Such oil finishes, pigments, and fillers require additional processing steps and can impart undesirable properties to the final fiber. Many water-dispersible polymers also require alkaline solutions for their removal which can cause degradation of the other polymer components of the fiber such as, for example, reduction of inherent viscosity, tenacity, and melt strength. Further, some water-dispersible polymers can not withstand exposure to water during hydroentanglement and, thus, are not suitable for the manufacture of nonwoven webs and fabrics.
Alternatively, the water-dispersible component may serve as a bonding agent for the thermoplastic fibers in nonwoven webs. Upon exposure to water, the fiber to fiber bonds come apart such that the nonwoven web loses its integrity and breaks down into individual fibers. The thermoplastic fiber components of these nonwoven webs, however, are not water-dispersible and remain present in the aqueous medium and, thus, must eventually be removed from municipal wastewater treatment plants. Hydroentanglement may be used to produce disintegratable nonwoven fabrics without or with very low levels (< 5 wt%) of added binder to hold the fibers together. Although these fabrics may disintegrate upon disposal, they often utilize fibers that are not water soluble or water-dispersible and may result in entanglement and plugging within sewer systems. Any added water-dispersible binders also must be minimally affected by hydroentangling and not form gelatinous buildup or cross-link, and thereby contribute to fabric handling or sewer related problems.
A few water-soluble or water-dispersible polymers are available, but are generally not applicable to melt blown fiber forming operations or melt spinning in general. Polymers, such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylic acid are not melt processable as a result of thermal decomposition that occurs at temperatures below the point where a suitable melt viscosity is attained. High molecular weight polyethylene oxide may have suitable thermal stability, but would provide a high viscosity solution at the polymer interface resulting in a slow rate of disintegration. Water-dispersible sulfopolyesters have been described, for example, in U.S. Patent No.'s 6,171,685; 5,543,488; 5,853,701 ; 4,304,901; 6,211,309; 5,570,605; 6,428,900; and 3,779,993. Typical sulfopolyesters, however, are low molecular weight thermoplastics that are brittle and lack the flexibility to withstand a winding operation to yield a roll of material that does not fracture or crumble. Sulfopolyesters also can exhibit blocking or fusing during processing into film or fibers, which may require the use of oil finishes or large amounts of pigments or fillers to avoid. Low molecular weight polyethylene oxide (more commonly known as polyethylene glycol) is a weak/brittle polymer that also does not have the required physical properties for fiber applications. Forming fibers from known water-soluble polymers via solution techniques is an alternative, but the added complexity of removing solvent, especially water, increases manufacturing costs.
Accordingly, there is a need for a water-dispersible fiber and fibrous articles prepared therefrom that exhibit adequate tensile strength, absorptivity, flexibility, and fabric integrity in the presence of moisture, especially upon exposure to human bodily fluids. In addition, a fibrous article is needed that does not require a binder and completely disperses or dissolves in residential or municipal sewerage systems. Potential uses include, but are not limited to, melt blown webs, spunbond fabrics, hydroentangled fabrics, wet-laid nonwovens, dry-laid non-wovens, bicomponent fiber components, adhesive promoting layers, binders for cellulosics, flushable nonwovens and films, dissolvable binder fibers, protective layers, and carriers for active ingredients to be released or dissolved in water. There is also a need for multicomponent fiber having a water-dispersible component that does not exhibit excessive blocking or fusing of filaments during spinning operations, is easily removed by hot water at neutral or slightly acidic pH, and is suitable for hydroentangling processes to manufacture nonwoven fabrics. These multicomponent fibers can be utilized to produce microfibers that can be used to produce various articles. Other extrudable and melt spun fibrous materials are also possible.
SUMMARY OF THE INVENTION
We have unexpectedly discovered that flexible, water-dispersible fibers may be prepared from sulfopolyesters. Thus the present invention provides a water- dispersible fiber comprising:
(A) a sulfopolyester having a glass transition temperature (Tg) of at least 250C, the sulfopolyester comprising:
(i) residues of one or more dicarboxylic acids;
(ii) about 4 to about 40 mole%, based on the total repeating units, of residues of at least one sulfomonomer having 2 functional groups and one or more sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
(iii) one or more diol residues wherein at least 25 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500; and (iv) 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
(B) optionally, a water-dispersible polymer blended with the sulfopolyester; and
(C) optionally, a water non-dispersible polymer blended with the sulfopolyester with the proviso that the blend is an immiscible blend; wherein the fiber contains less than 10 weight percent of a pigment or filler, based on the total weight of the fiber.
The fibers of the present invention may be unicomponent fibers that rapidly disperse or dissolve in water and may be produced by melt-blowing or melt-spinning. The fibers may be prepared from a single sulfopolyester or a blend of the sulfopolyester with a water-dispersible or water non-dispersible polymer. Thus, the fiber of the present invention, optionally, may include a water-dispersible polymer blended with the sulfopolyester. In addition, the fiber may optionally include a water non-dispersible polymer blended with the sulfopolyester, provided that the blend is an immiscible blend. Our invention also includes fibrous articles comprising our water- dispersible fibers. Thus, the fibers of our invention may be used to prepare various fibrous articles, such as yarns, melt-blown webs, spunbonded webs, and nonwoven fabrics that are, in turn, water-dispersible or flushable. Staple fibers of our invention can also be blended with natural or synthetic fibers in paper, nonwoven webs, and textile yarns.
Another aspect of the present invention is a water-dispersible fiber comprising:
(A) a sulfopolyester having a glass transition temperature (Tg) of at least 250C, the sulfopolyester comprising:
(i) about 50 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid, based on the total acid residues; (ii) about 4 to about 30 mole%, based on the total acid residues, of a residue of sodiosulfoisophthalic acid;
(iii) one or more diol residues wherein at least 25 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500;
(iv) 0 to about 20 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
(B) optionally, a first water-dispersible polymer blended with the sulfopolyester; and
(C) optionally, a water non-dispersible polymer blended with the sulfopolyester to form a blend with the proviso that the blend is an immiscible blend; wherein the fiber contains less than 10 weight percent of a pigment or filler, based on the total weight of the fiber.
The water-dispersible, fibrous articles of the present invention include personal care articles such as, for example, wipes, gauze, tissue, diapers, training pants, sanitary napkins, bandages, wound care, and surgical dressings. In addition to being water-dispersible, the fibrous articles of our invention are flushable, that is, compatible with and suitable for disposal in residential and municipal sewerage systems.
The present invention also provides a multicomponent fiber comprising a water-dispersible sulfopolyester and one or more water non-dispersible polymers. The fiber has an engineered geometry such that the water non-dispersible polymers are present as segments substantially isolated from each other by the intervening sulfopolyester, which acts as a binder or encapsulating matrix for the water non- dispersible segments. Thus, another aspect of our invention is a multicomponent fiber having a shaped cross section, comprising:
(A) a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 570C, the sulfopolyester comprising: (i) residues of one or more dicarboxylic acids;
(ii) about 4 to about 40 mole%, based on the total repeating units, of residues of at least one sulfomonomer having 2 functional groups and one or more sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
(iii) one or more diol residues wherein at least 25 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500; and
(iv) 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof; and (B) a plurality of segments comprising one or more water non-dispersible polymers immiscible with the sulfopolyester, wherein the segments are substantially isolated from each other by the sulfopolyester intervening between the segments; wherein the fiber contains less than 10 weight percent of a pigment or filler, based on the total weight of the fiber.
The sulfopolyester has a glass transition temperature of at least 570C which greatly reduces blocking and fusion of the fiber during winding and long term storage.
The sulfopolyester may be removed by contacting the multicomponent fiber with water to leave behind the water non-dispersible segments as microdenier fibers. Our invention, therefore, also provides a process for microdenier fibers comprising: (A) spinning a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 570C and one or more water non-dispersible polymers immiscible with the sulfopolyester into multicomponent fibers, the sulfopolyester comprising:
(i) about 50 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid, based on the total acid residues;
(ii) about 4 to about 30 mole%, based on the total acid residues, of a residue of sodiosulfoisophthalic acid; (iii) one or more diol residues wherein at least 25 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500; and
(iv) 0 to about 20 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof; wherein the fibers have a plurality of segments comprising the water non-dispersible polymers wherein the segments are substantially isolated from each other by the sulfopolyester intervening between the segments and the fibers contain less than 10 weight percent of a pigment or filler, based on the total weight of the fibers; and (B) contacting the multicomponent fibers with water to remove the sulfopolyester thereby forming microdenier fibers.
The water non-dispersible polymers may be biodistintegratable as determined by DIN Standard 54900 and/or biodegradable as determined by ASTM Standard Method, D6340-98. The multicomponent fiber also may be used to prepare a fibrous article such as a yarn, fabric, melt-blown web, spun-bonded web, or non-woven fabric and which may comprise one or more layers of fibers. The fibrous article having multicomponent fibers, in turn, may be contacted with water to produce fibrous articles containing microdenier fibers.
Thus, another aspect of the invention is a process for a microdenier fiber web, comprising:
(A) spinning a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 570C and one or more water non-dispersible polymers immiscible with the sulfopolyester into multicomponent fibers, the sulfopolyester comprising:
(i) about 50 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid, based on the total acid residues;
(ii) about 4 to about 30 mole%, based on the total acid residues, of a residue of sodiosulfoisophthalic acid; (iii) one or more diol residues wherein at least 25 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500; and
(iv) 0 to about 20 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof. wherein the multicomponent fibers have a plurality of segments comprising the water non-dispersible polymers and the segments are substantially isolated from each other by the sulfopolyester intervening between the segments and the fibers contain less than 10 weight percent of a pigment or filler, based on the total weight of said fibers;
(B) overlapping and collecting the multicomponent fibers of Step A to form a nonwoven web; and
(C) contacting the nonwoven web with water to remove the sulfopolyester thereby forming a microdenier fiber web.
Our invention also provides a process making a water-dispersible, nonwoven fabric comprising:
(A) heating a water-dispersible polymer composition to a temperature above its flow point, wherein the polymer composition comprises
(i) a sulfopolyester having a glass transition temperature (Tg) of at least 250C, the sulfopolyester comprising:
(a) residues of one or more dicarboxylic acids;
(b) about 4 to about 40 mole%, based on the total repeating units, of residues of at least one sulfomonomer having 2 functional groups and one or more metal sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
(c) one or more diol residues wherein at least 20 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500; (d) 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
(ii) optionally, a water-dispersible polymer blended with the sulfopolyester; and
(iii) optionally, a water non-dispersible polymer blended with the sulfopolyester to form a blend with the proviso that the blend is an immiscible blend; wherein the polymer composition contains less than 10 weight percent of a pigment or filler, based on the total weight of the polymer composition;
(B) melt spinning filaments; and
(C) overlapping and collecting the filaments of Step B to form a nonwoven web. In another aspect of the present invention, there is provided a multicomponent fiber, having a shaped cross section, comprising:
(A) at least one water dispersible sulfopolyester; and
(B) a plurality of microfiber domains comprising one or more water non- dispersible polymers immiscible with the sulfopolyester, wherein the domains are substantially isolated from each other by the sulfopolyester intervening between the domains, wherein the fiber has an as-spun denier of less than about 6 denier per filament; wherein the water dispersible sulfopolyesters exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprises less than about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residues.
In another aspect of the present invention, there is provided a multicomponent extrudate having a shaped cross section, comprising:
(A) at least one water dispersible sulfopolyester; and
(B) a plurality of domains comprising one or more water non-dispersible polymers immiscible with the sulfopolyester, wherein the domains are substantially isolated from each other by the sulfopolyester intervening between the domains, wherein the extrudate is capable of being melt drawn at a speed of at least about 2000 m/min. In another aspect of the present invention, there is provided a process for making a multicomponent fiber having a shaped cross section comprising spinning at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with the sulfopolyester, wherein the multicomponent fiber has a plurality of domains comprising the water non-dispersible polymers and the domains are substantially isolated from each other by the sulfopolyester intervening between the domains; wherein the multicomponent fiber has an as-spun denier of less than about 6 denier per filament; wherein the water dispersible sulfopolyester exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprises less than about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residues.
In another aspect of the invention, there is provided a process for making a multicomponent fiber having a shaped cross section comprising extruding at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with the sulfopolyester to produce a multicomponent extrudate, wherein the multicomponent extrudate has a plurality of domains comprising said water non-dispersible polymers and said domains are substantially isolated from each other by said sulfopolyester intervening between said domains; and melt drawing the multicomponent extrudate at a speed of at least about 2000 m/min to produce the multicomponent fiber.
In another aspect, the present invention provides a process for producing microdenier fibers comprising:
(A) spinning at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with the water dispersible sulfopolyester into multicomponent fibers, wherein the multicomponent fibers have a plurality of domains comprising the water non-dispersible polymers wherein the domains are substantially isolated from each other by the sulfopolyester intervening between said domains; wherein the multicomponent fiber has an as-spun denier of less than about 6 denier per filament; wherein said water dispersible sulfopolyester exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprises less than about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residues; and
(B) contacting the multicomponent fibers with water to remove said water dispersible sulfopolyester thereby forming microdenier fibers of the water non- dispersible polymer(s).
In another aspect, the present invention provides a process for producing microdenier fibers comprising:
(A) extruding at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with the water dispersible sulfopolyester to produce multicomponent extrudates, wherein the multicomponent extrudates have a plurality of domains comprising the water non-dispersible polymers wherein the domains are substantially isolated from each other by the sulfopolyester intervening between the domains;
(B) melt drawing the multicomponent extrudates at a speed of at least about 2000 m/min to form multicomponent fibers; and
(C) contacting the multicomponent fibers with water to remove the water dispersible sulfopolyester thereby forming microdenier fibers of the water non- dispersible polymer(s).
In another aspect of this invention, a process is provided for making a microdenier fiber web comprising:
(A) spinning at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with the sulfopolyester into multicomponent fibers, the multicomponent fibers have a plurality of domains comprising the water non-dispersible polymers wherein the domains are substantially isolated from each other by the water dispersible sulfopolyester intervening between the domains; wherein the multicomponent fiber has an as-spun denier of less than about 6 denier per filament; wherein the water dispersible sulfopolyester exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprising less than, about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residues;
(B) collecting the multicomponent fibers of Step (A) to form a non-woven web; and
(C) contacting the non-woven web with water to remove the sulfopolyester thereby forming a microdenier fiber web.
In another aspect of this invention, a process for making a microdenier fiber web is provided comprising:
(A) extruding at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with the sulfopolyester to a produce multicomponent extrudate, the multicomponent extrudate have a plurality of domains comprising the water non-dispersible polymers wherein the domains are substantially isolated from each other by the sulfopolyester intervening between the domains;
(B) melt drawing the multicomponent extrudates at a speed of at least about 2000 m/min to form multicomponent fibers;
(C) collecting the multicomponent fibers of Step (B) to form a non-woven web; and
(D) contacting the non-woven web with water to remove said sulfopolyester thereby forming a microdenier fiber web.
In another embodiment of this invention, a process for producing a water non- dispersible polymer microfiber is provided, the process comprising: a) cutting a multicomponent fiber into cut multicomponent fibers; b) contacting a fiber-containing feedstock with water to produce a fiber mix slurry; wherein the fiber-containing feedstock comprises cut multicomponent fibers; c) heating the fiber mix slurry to produce a heated fiber mix slurry; d) optionally, mixing the fiber mix slurry in a shearing zone; e) removing at least a portion of the sulfopolyester from the multicomponent fiber to produce a slurry mixture comprising a sulfopolyester dispersion and the water non-dispersible polymer microfibers; and f) separating the water non-dispersible polymer microfibers from the slurry mixture.
In another embodiment of this invention, the water non-dispersible polymer microfϊber is provided comprising at least one water non-dispersible polymer wherein the water non-dispersible polymer microfiber has an equivalent diameter of less than 5 microns and length of less than 25 millimeters.
In another embodiment of this invention, a process for producing a nonwoven article from the water non-dispersible polymer microfiber is provided, the process comprising: a) providing a water non-dispersible polymer microfiber produced from a multicomponent fiber; and b) producing the nonwoven article utilizing a wet-laid process or a dry-laid process.
DETAILED DESCRIPTION
The present invention provides water-dispersible fibers and fibrous articles that show tensile strength, absorptivity, flexibility, and fabric integrity in the presence of moisture, especially upon exposure to human bodily fluids. The fibers and fibrous articles of our invention do not require the presence of oil, wax, or fatty acid finishes or the use of large amounts (typically 10 wt% or greater) of pigments or fillers to prevent blocking or fusing of the fibers during processing. In addition, the fibrous articles prepared from our novel fibers do not require a binder and readily disperse or dissolve in home or public sewerage systems.
In a general embodiment, our invention provides a water-dispersible fiber comprising a sulfopolyester having a glass transition temperature (Tg) of at least 250C, wherein the sulfopolyester comprises: (A) residues of one or more dicarboxylic acids; (B) about 4 to about 40 mole%, based on the total repeating units, of residues of at least one sulfomonomer having 2 functional groups and one or more sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
(C) one or more diol residues wherein at least 25 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500; and (iv) 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof. Our fiber may optionally include a water-dispersible polymer blended with the sulfopolyester and, optionally, a water non-dispersible polymer blended with the sulfopolyester with the proviso that the blend is an immiscible blend. Our fiber contains less than 10 weight percent of a pigment or filler, based on the total weight of the fiber. The present invention also includes fibrous articles comprising these fibers and may include personal care products such as wipes, gauze, tissue, diapers, adult incontinence briefs, training pants, sanitary napkins, bandages, and surgical dressings. The fibrous articles may have one or more absorbent layers of fibers.
The fibers of our invention may be unicomponent fibers, bicomponent or multicomponent fibers. For example, the fibers of the present invention may be prepared by melt spinning a single sulfopolyester or sulfopolyester blend and include staple, monofilament, and multifilament fibers with a shaped cross-section. In addition, our invention provides multicomponent fibers, such as described, for example, in U.S. Patent No. 5,916,678, which may be prepared by extruding the sulfopolyester and one or more water non-dispersible polymers, which are immiscible with the sulfopolyester, separately through a spinneret having a shaped or engineered transverse geometry such as, for example, an "islands-in-the-sea", sheath-core, side- by-side, or segmented pie configuration. The sulfopolyester may be later removed by dissolving the interfacial layers or pie segments and leaving the smaller filaments or microdenier fibers of the water non-dispersible polymer(s). These fibers of the water non-dispersible polymer have fiber size much smaller than the multi-component fiber before removing the sulfopolyester. For example, the sulfopolyester and water non- dispersible polymers may be fed to a polymer distribution system where the polymers are introduced into a segmented spinneret plate. The polymers follow separate paths to the fiber spinneret and are combined at the spinneret hole which comprises either two concentric circular holes thus providing a sheath-core type fiber, or a circular spinneret hole divided along a diameter into multiple parts to provide a fiber having a side-by-side type. Alternatively, the immiscible water dispersible sulfopolyester and water non-dispersible polymers may be introduced separately into a spinneret having a plurality of radial channels to produce a multicomponent fiber having a segmented pie cross section. Typically, the sulfopolyester will form the "sheath" component of a sheath core configuration. In fiber cross sections having a plurality of segments, the water non-dispersible segments, typically, are substantially isolated from each other by the sulfopolyester. Alternatively, multicomponent fibers may be formed by melting the sulfopolyester and water non-dispersible polymers in separate extruders and directing the polymer flows into one spinneret with a plurality of distribution flow paths in form of small thin tubes or segments to provide a fiber having an islands-in- the-sea shaped cross section. An example of such a spinneret is described in U.S. Patent No. 5,366,804. In the present invention, typically, the sulfopolyester will form the "sea" component and the water non-dispersible polymer will form the "islands" component.
Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Further, the ranges stated in this disclosure and the claims are intended to include the entire range specifically and not just the endpoint(s). For example, a range stated to be 0 to 10 is intended to disclose all whole numbers between 0 and 10 such as, for example 1, 2, 3, 4, etc., all fractional numbers between 0 and 10, for example 1.5, 2.3, 4.57, 6.1113, etc., and the endpoints 0 and 10. Also, a range associated with chemical substituent groups such as, for example, "Cl to C5 hydrocarbons", is intended to specifically include and disclose Cl and C5 hydrocarbons as well as C2, C3, and C4 hydrocarbons.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
The unicomponent fibers and fibrous articles produced from the unicomponent fibers of the present invention are water-dispersible and, typically, completely disperse at room temperature. Higher water temperatures can be used to accelerate their dispersibility or rate of removal from the nonwoven or multicomponent fiber. The term "water-dispersible", as used herein with respect to unicomponent fibers and fibrous articles prepared from unicomponent fibers, is intended to be synonymous with the terms "water-dissipatable", "water-disintegratable", "water-dissolvable", "water-dispellable", "water soluble", water-removable", "hydrosoluble", and "hydrodispersible" and is intended to mean that the fiber or fibrous article is therein or therethrough dispersed or dissolved by the action of water. The terms "dispersed", "dispersible","dissipate", or "dissipatable" mean that, using a sufficient amount of deionized water (e.g., 100:1 water.fiber by weight) to form a loose suspension or slurry of the fibers or fibrous article, at a temperature of about 6O0C, and within a time period of up to 5 days, the fiber or fibrous article dissolves, disintegrates, or separates into a plurality of incoherent pieces or particles distributed more or less throughout the medium such that no recognizable filaments are recoverable from the medium upon removal of the water, for example, by filtration or evaporation. Thus, "water- dispersible", as used herein, is not intended to include the simple disintegration of an assembly of entangled or bound, but otherwise water insoluble or nondispersible, fibers wherein the fiber assembly simply breaks apart in water to produce a slurry of fibers in water which could be recovered by removal of the water. In the context of this invention, all of these terms refer to the activity of water or a mixture of water and a water-miscible cosolvent on the sulfopolyesters described herein. Examples of such water-miscible cosolvents includes alcohols, ketones, glycol ethers, esters and the like. It is intended for this terminology to include conditions where the sulfopolyester is dissolved to form a true solution as well as those where the sulfopolyester is dispersed within the aqueous medium. Often, due to the statistical nature of sulfopolyester compositions, it is possible to have a soluble fraction and a dispersed fraction when a single sulfopolyester sample is placed in an aqueous medium.
Similarly, the term "water-dispersible", as used herein in reference to the sulfopolyester as one component of a multicomponent fiber or fibrous article, also is intended to be synonymous with the terms "water-dissipatable", "water- disintegratable", "water-dissolvable", "water-dispellable", "water soluble", "water- removable", "hydrosoluble", and "hydrodispersible" and is intended to mean that the sulfopolyester component is sufficiently removed from the multicomponent fiber and is dispersed or dissolved by the action of water to enable the release and separation of the water non-dispersible fibers contained therein. The terms "dispersed", "dispersible", "dissipate", or "dissipatable" mean that, using a sufficient amount of deionized water (e.g., 100:1 wateπfiber by weight) to form a loose suspension or slurry of the fibers or fibrous article, at a temperature of about 6O0C, and within a time period of up to 5 days, sulfopolyester component dissolves, disintegrates, or separates from the multicomponent fiber, leaving behind a plurality of microdenier fibers from the water non-dispersible segments.
The term "segment" or "domain" or "zone" when used to describe the shaped cross section of a multicomponent fiber refers to the area within the cross section comprising the water non-dispersible polymers where these domains or segments are substantially isolated from each other by the water-dispersible sulfopolyester intervening between the segments or domains. The term "substantially isolated", as used herein, is intended to mean that the segments or domains are set apart from each other to permit the segments domains to form individual fibers upon removal of the sulfopolyester. Segments or domains or zones can be of similar size and shape or varying size and shape. Again, segments or domains or zones can be arranged in any configuration. These segments or domains or zones are "substantially continuous" along the length of the multicomponent extrudate or fiber. The term "substantially continuous" means continuous along at least 10 cm length of the multicomponent fiber. These segments, domains, or zones of the multicomponent fiber produce water non-dispersible polymer microfibers when the water dispersible sulfopolyester is removed.
As stated within this disclosure, the shaped cross section of a multicomponent fiber can, for example, be in the form of a sheath core, islands-in-the sea, segmented pie, hollow segmented pie; off-centered segmented pie, etc..
The water-dispersible fiber of the present invention is prepared from polyesters or, more specifically sulfopolyesters, comprising dicarboxylic acid monomer residues, sulfomonomer residues, diol monomer residues, and repeating units. The sulfomonomer may be a dicarboxylic acid, a diol, or hydroxycarboxylic acid. Thus, the term "monomer residue", as used herein, means a residue of a dicarboxylic acid, a diol, or a hydroxycarboxylic acid. A "repeating unit", as used herein, means an organic structure having 2 monomer residues bonded through a carbonyloxy group. The sulfopolyesters of the present invention contain substantially equal molar proportions of acid residues (100 mole %) and diol residues (100 mole %) which react in substantially equal proportions such that the total moles of repeating units is equal to 100 mole %. The mole percentages provided in the present disclosure, therefore, may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units. For example, a sulfopolyester containing 30 mole% of a sulfomonomer, which may be a dicarboxylic acid, a diol, or hydroxycarboxylic acid, based on the total repeating units, means that the sulfopolyester contains 30 mole% sulfomonomer out of a total of 100 mole% repeating units. Thus, there are 30 moles of sulfomonomer residues among every 100 moles of repeating units. Similarly, a sulfopolyester containing 30 mole% of a dicarboxylic acid sulfomonomer, based on the total acid residues, means the sulfopolyester contains 30 mole% sulfomonomer out of a total of 100 mole% acid residues. Thus, in this latter case, there are 30 moles of sulfomonomer residues among every 100 moles of acid residues.
The sulfopolyesters described herein have an inherent viscosity, abbreviated hereinafter as "Ih.V.", of at least about 0.1 dL/g, preferably about 0.2 to 0.3 dL/g, and most preferably greater than about 0.3 dL/g, measured in a 60/40 parts by weight solution of phenol/tetrachloroethane solvent at 250C and at a concentration of about 0.5 g of sulfopolyester in 100 mL of solvent. The term "polyester", as used herein, encompasses both "homopolyesters" and "copolyesters" and means a synthetic polymer prepared by the polycondensation of difunctional carboxylic acids with difunctional hydroxyl compound. As used herein, the term "sulfopolyester" means any polyester comprising a sulfomonomer. Typically the difunctional carboxylic acid is a dicarboxylic acid and the difunctional hydroxyl compound is a dihydric alcohol such as, for example glycols and diols. Alternatively, the difunctional carboxylic acid may be a hydroxy carboxylic acid such as, for example, p-hydroxybenzoic acid, and the difunctional hydroxyl compound may be a aromatic nucleus bearing 2 hydroxy substituents such as, for example, hydroquinone. The term "residue", as used herein, means any organic structure incorporated into the polymer through a polycondensation reaction involving the corresponding monomer. Thus, the dicarboxylic acid residue may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof. As used herein, therefore, the term dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half- esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process with a diol to make a high molecular weight polyester.
The sulfopolyester of the present invention includes one or more dicarboxylic acid residues. Depending on the type and concentration of the sulfomonomer, the dicarboxylic acid residue may comprise from about 60 to about 100 mole% of the acid residues. Other examples of concentration ranges of dicarboxylic acid residues are from about 60 mole% to about 95 mole%, and about 70 mole% to about 95 mole%. Examples of dicarboxylic acids that may be used include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, or mixtures of two or more of these acids. Thus, suitable dicarboxylic acids include, but are not limited to, succinic; glutaric; adipic; azelaic; sebacic; fumaric; maleic; itaconic; 1,3-cyclohexanedicarboxylic; 1,4-cyclohexanedicarboxylic; diglycolic; 2,5- norbornanedicarboxylic; phthalic; terephthalic; 1,4-naphthalenedicarboxylic; 2,5- naphthalenedicarboxylic; diphenic; 4,4'-oxydibenzoic; 4,4'-sulfonyidibenzoic; and isophthalic. The preferred dicarboxylic acid residues are isophthalic, terephthalic, and 1,4-cyclohexanedicarboxylic acids, or if diesters are used, dimethyl terephthalate, dimethyl isophthalate, and dimethyl-l,4-cyclohexanedicarboxylate with the residues of isophthalic and terephthalic acid being especially preferred. Although the dicarboxylic acid methyl ester is the most preferred embodiment, it is also acceptable to include higher order alkyl esters, such as ethyl, propyl, isopropyl, butyl, and so forth. In addition, aromatic esters, particularly phenyl, also may be employed.
The sulfopolyester includes about 4 to about 40 mole%, based on the total repeating units, of residues of at least one sulfomonomer having 2 functional groups and one or more sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof. Additional examples of concentration ranges for the sulfomonomer residues are about 4 to about 35 mole%, about 8 to about 30 mole%, and about 8 to about 25 mole%, based on the total repeating units. The sulfomonomer may be a dicarboxylic acid or ester thereof containing a sulfonate group, a diol containing a sulfonate group, or a hydroxy acid containing a sulfonate group. The term "sulfonate" refers to a salt of a sulfonic acid having the structure "-SO3M" wherein M is the cation of the sulfonate salt. The cation of the sulfonate salt may be a metal ion such as Li+, Na+, K+, Mg+^ Ca^+, Ni+"1", Fe+"1", and the like. Alternatively, the cation of the sulfonate salt may be non-metallic such as a nitrogenous base as described, for example, in U.S. Patent No. 4,304,901. Nitrogen- based cations are derived from nitrogen-containing bases, which may be aliphatic, cycloaliphatic, or aromatic compounds. Examples of such nitrogen containing bases include ammonia, dimethylethanolamine, diethanolamine, triethanolamine, pyridine, morpholine, and piperidine. Because monomers containing the nitrogen-based sulfonate salts typically are not thermally stable at conditions required to make the polymers in the melt, the method of this invention for preparing sulfopolyesters containing nitrogen-based sulfonate salt groups is to disperse, dissipate, or dissolve the polymer containing the required amount of sulfonate group in the form of its alkali metal salt in water and then exchange the alkali metal cation for a nitrogen-based cation.
When a monovalent alkali metal ion is used as the cation of the sulfonate salt, the resulting sulfopolyester is completely dispersible in water with the rate of dispersion dependent on the content of sulfomonomer in the polymer, temperature of the water, surface area/thickness of the sulfopolyester, and so forth. When a divalent metal ion is used, the resulting sulfopolyesters are not readily dispersed by cold water but are more easily dispersed by hot water. Utilization of more than one counterion within a single polymer composition is possible and may offer a means to tailor or fine-tune the water-responsivity of the resulting article of manufacture. Examples of sulfomonomers residues include monomer residues where the sulfonate salt group is attached to an aromatic acid nucleus, such as, for example, benzene; naphthalene; diphenyl; oxydiphenyl; sulfonyldiphenyl; and methylenediphenyl or cycloaliphatic rings, such as, for example, cyclohexyl; cyclopentyl; cyclobutyl; cycloheptyl; and cyclooctyl. Other examples of sulfomonomer residues which may be used in the present invention are the metal sulfonate salt of sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalic acid, or combinations thereof. Other examples of sulfomonomers which may be used are 5-sodiosulfoisophthalic acid and esters thereof. If the sulfomonomer residue is from 5-sodiosulfoisophthalic acid, typical sulfomonomer concentration ranges are about 4 to about 35 mole%, about 8 to about 30 mole %, and about 8 to 25 mole %, based on the total moles of acid residues. The sulfomonomers used in the preparation of the sulfopoly esters are known compounds and may be prepared using methods well known in the art. For example, sulfomonomers in which the sulfonate group is attached to an aromatic ring may be prepared by sulfonating the aromatic compound with oleum to obtain the corresponding sulfonic acid and followed by reaction with a metal oxide or base, for example, sodium acetate, to prepare the sulfonate salt. Procedures for preparation of various sulfomonomers are described, for example, in U.S. Patent No.'s 3,779,993; 3,018,272; and 3,528,947.
It is also possible to prepare the polyester using, for example, a sodium sulfonate salt, and ion-exchange methods to replace the sodium with a different ion, such as zinc, when the polymer is in the dispersed form. This type of ion exchange procedure is generally superior to preparing the polymer with divalent salts insofar as the sodium salts are usually more soluble in the polymer reactant melt-phase.
The sulfopolyester includes one or more diol residues which may include aliphatic, cycloaliphatic, and aralkyl glycols. The cycloaliphatic diols, for example, 1,3- and 1 ,4-cyclohexanedimethanol, may be present as their pure cis or trans isomers or as a mixture of cis and trans isomers. As used herein, the term "diol" is synonymous with the term "glycol" and means any dihydric alcohol. Examples of diols include, but are not limited to, ethylene glycol; diethylene glycol; triethylene glycol; polyethylene glycols; 1 ,3-propanediol; 2,4-dimethyl-2-ethylhexane-l,3-diol; 2,2-dimethyl- 1 ,3-propanediol; 2-ethyl-2-butyl- 1 ,3-propanediol; 2-ethyl-2-isobutyl- 1,3-propanediol; 1 ,3-butanediol; 1,4-butanediol; 1,5-pentanediol; 1 ,6-hexanediol; 2,2,4-trimethyl-l,6-hexanediol; thiodiethanol; 1 ,2-cyclohexanedimethanol; 1,3- cyclohexanedimethanol; 1 ,4-cyclohexanedimethanol; 2,2,4,4-tetramethyl-l ,3- cyclobutanediol; p-xylylenediol, or combinations of one or more of these glycols.
The diol residues may include from about 25 mole% to about 100 mole%, based on the total diol residues, of residue of a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500. Non-limiting examples of lower molecular weight polyethylene glycols, e.g., wherein n is from 2 to 6, are diethylene glycol, triethylene glycol, and tetraethylene glycol. Of these lower molecular weight glycols, diethylene and triethylene glycol are most preferred. Higher molecular weight polyethylene glycols (abbreviated herein as "PEG"), wherein n is from 7 to about 500, include the commercially available products known under the designation C ARBO WAX®, a product of Dow Chemical Company (formerly Union Carbide). Typically, PEGs are used in combination with other diols such as, for example, diethylene glycol or ethylene glycol. Based on the values of n, which range from greater than 6 to 500, the molecular weight may range from greater than 300 to about 22,000 g/mol. The molecular weight and the mole% are inversely proportional to each other; specifically, as the molecular weight is increased, the mole % will be decreased in order to achieve a designated degree of hydrophilicity. For example, it is illustrative of this concept to consider that a PEG having a molecular weight of 1000 may constitute up to 10 mole% of the total diol, while a PEG having a molecular weight of 10,000 would typically be incorporated at a level of less than 1 mole% of the total diol.
Certain dimer, trimer, and tetramer diols may be formed in situ due to side reactions that may be controlled by varying the process conditions. For example, varying amounts of diethylene, triethylene, and tetraethylene glycols may be formed from ethylene glycol from an acid-catalyzed dehydration reaction which occurs readily when the polycondensation reaction is carried out under acidic conditions. The presence of buffer solutions, well-known to those skilled in the art, may be added to the reaction mixture to retard these side reactions. Additional compositional latitude is possible, however, if the buffer is omitted and the dimerization, trimerization, and tetramerization reactions are allowed to proceed.
The sulfopolyester of the present invention may include from 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof. Non-limiting examples of branching monomers are 1,1,1- trimethylol propane, 1,1 ,1-trimethylolethane, glycerin, pentaerythritol, erythritol, threitol, dipentaerythritol, sorbitol, trimellitic anhydride, pyromellitic dianhydride, dimethylol propionic acid, or combinations thereof. Further examples of branching monomer concentration ranges are from 0 to about 20 mole% and from 0 to about 10 mole%. The presence of a branching monomer may result in a number of possible benefits to the sulfopolyester of the present invention, including but not limited to, the ability to tailor rheological, solubility, and tensile properties. For example, at a constant molecular weight, a branched sulfopolyester, compared to a linear analog, will also have a greater concentration of end groups that may facilitate post- polymerization crosslinking reactions. At high concentrations of branching agent, however, the sulfopolyester may be prone to gelation.
The sulfopolyester used for the fiber of the present invention has a glass transition temperature, abbreviated herein as "Tg", of at least 250C as measured on the dry polymer using standard techniques, such as differential scanning calorimetry ("DSC"), well known to persons skilled in the art. The Tg measurements of the sulfopolyesters of the present invention are conducted using a "dry polymer", that is, a polymer sample in which adventitious or absorbed water is driven off by heating to polymer to a temperature of about 2000C and allowing the sample to return to room temperature. Typically, the sulfopolyester is dried in the DSC apparatus by conducting a first thermal scan in which the sample is heated to a temperature above the water vaporization temperature, holding the sample at that temperature until the vaporization of the water absorbed in the polymer is complete (as indicated by an a large, broad endotherm), cooling the sample to room temperature, and then conducting a second thermal scan to obtain the Tg measurement. Further examples of glass transition temperatures exhibited by the sulfopolyester are at least 3O0C, at least 350C, at least 4O0C, at least 5O0C, at least 6O0C, at least 650C, at least 8O0C, and at least 9O0C. Although other Tg's are possible, typical glass transition temperatures of the dry sulfopolyesters our invention are about 3O0C, about 480C, about 550C, about 65°C, about 7O0C, about 750C, about 850C, and about 9O0C.
Our novel fibers may consist essentially of or, consist of, the sulfopolyesters described hereinabove. In another embodiment, however, the sulfopolyesters of this invention may be a single polyester or may be blended with one or more supplemental polymers to modify the properties of the resulting fiber. The supplemental polymer may or may not be water-dispersible depending on the application and may be miscible or immiscible with the sulfopolyester. If the supplemental polymer is water non-dispersible, it is preferred that the blend with the sulfopolyester is immiscible. The term "miscible", as used herein, is intended to mean that the blend has a single, homogeneous amorphous phase as indicated by a single composition-dependent Tg. For example, a first polymer that is miscible with second polymer may be used to "plasticize" the second polymer as illustrated, for example, in U.S. Patent No. 6,21 1,309. By contrast, the term "immiscible", as used herein, denotes a blend that shows at least 2, randomly mixed, phases and exhibits more than one Tg. Some polymers may be immiscible and yet compatible with the sulfopolyester. A further general description of miscible and immiscible polymer blends and the various analytical techniques for their characterization may be found in Polymer Blends Volumes 1 and 2, Edited by D.R. Paul and CB. Bucknall, 2000, John Wiley & Sons, Inc.
Non-limiting examples of water-dispersible polymers that may be blended with the sulfopolyester are polymethacrylic acid, polyvinyl pyrrolidone, polyethylene- acrylic acid copolymers, polyvinyl methyl ether, polyvinyl alcohol, polyethylene oxide, hydroxy propyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, isopropyl cellulose, methyl ether starch, polyacrylamides, poly(N-vinyl caprolactam), polyethyl oxazoline, poly(2-isopropyl-2- oxazoline), polyvinyl methyl oxazolidone, water-dispersible sulfopolyesters, polyvinyl methyl oxazolidimone, poly(2,4-dimethyl-6-triazinylethylene), and ethylene oxide-propylene oxide copolymers. Examples of polymers which are water non- dispersible that may be blended with the sulfopolyester include, but are not limited to, polyolefins, such as homo- and copolymers of polyethylene and polypropylene; poly(ethylene terephthalate); poly(butylene terephthalate); and polyamides, such as nylon-6; polylactides; caprolactone; Eastar Bio® (poly(tetramethylene adipate-co- terephthalate), a product of Eastman Chemical Company); polycarbonate; polyurethane; and polyvinyl chloride.
According to our invention, blends of more than one sulfopolyester may be used to tailor the end-use properties of the resulting fiber or fibrous article, for example, a nonwoven fabric or web. The blends of one or more sulfopolyesters will have Tg' s of at least 250C for the water-dispersible, unicomponent fibers and at least 570C for the multicomponent fibers. Thus, blending may also be exploited to alter the processing characteristics of a sulfopolyester to facilitate the fabrication of a nonwoven. In another example, an immiscible blend of polypropylene and sulfopolyester may provide a conventional nonwoven web that will break apart and completely disperse in water as true solubility is not needed. In this latter example, the desired performance is related to maintaining the physical properties of the polypropylene while the sulfopolyester is only a spectator during the actual use of the product or, alternatively, the sulfopolyester is fugitive and is removed before the final form of the product is utilized.
The sulfopolyester and supplemental polymer may be blended in batch, semicontinuous, or continuous processes. Small scale batches may be readily prepared in any high-intensity mixing devices well-known to those skilled in the art, such as Banbury mixers, prior to melt-spinning fibers. The components may also be blended in solution in an appropriate solvent. The melt blending method includes blending the sulfopolyester and supplemental polymer at a temperature sufficient to melt the polymers. The blend may be cooled and pelletized for further use or the melt blend can be melt spun directly from this molten blend into fiber form. The term "melt" as used herein includes, but is not limited to, merely softening the polyester. For melt mixing methods generally known in the polymers art, see Mixing and Compounding of Polymers (I. Manas-Zloczower & Z. Tadmor editors, Carl Hanser Verlag Publisher, 1994, New York, N. Y.).
Our invention also provides a water-dispersible fiber comprising a sulfopolyester having a glass transition temperature (Tg) of at least 250C, wherein the sulfopolyester comprises: (A) about 50 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid, based on the total acid residues;
(B) about 4 to about 30 mole%, based on the total acid residues, of a residue of sodiosulfoisophthalic acid;
(C) one or more diol residues wherein at least 25 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500; (iv) 0 to about 20 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof. As described hereinabove, the fiber may optionally include a first water-dispersible polymer blended with the sulfopolyester; and, optionally, a water non-dispersible polymer blended with the sulfopolyester such that the blend is an immiscible blend. Our fiber contains less than 10 weight percent of a pigment or filler, based on the total weight of the fiber. The first water-dispersible polymer is as described hereinabove. The sulfopolyester should have a glass transition temperature (Tg) of at least 250C, but may have, for example, a Tg of about 350C, about 480C, about 550C, about 650C, about 7O0C, about 750C, about 850C, and about 9O0C. The sulfopolyester may contain other concentrations of isophthalic acid residues, for example, about 60 to about 95 mole%, and about 75 to about 95 mole%. Further examples of isophthalic acid residue concentrations ranges are about 70 to about 85 mole%, about 85 to about 95 mole% and about 90 to about 95 mole%. The sulfopolyester also may comprise about 25 to about 95 mole% of the residues of diethylene glycol. Further examples of diethylene glycol residue concentration ranges include about 50 to about 95 mole%, about 70 to about 95 mole%, and about 75 to about 95 mole%. The sulfopolyester also may include the residues of ethylene glycol and/or 1,4-cyclohexanedimethanol, abbreviated herein as "CHDM". Typical concentration ranges of CHDM residues are about 10 to about 75 mole%, about 25 to about 65 mole%, and about 40 to about 60 mole%. Typical concentration ranges of ethylene glycol residues are about 10 to about 75 mole%, about 25 to about 65 mole%, and about 40 to about 60 mole%. In another embodiment, the sulfopolyester comprises is about 75 to about 96 mole% of the residues of isophthalic acid and about 25 to about 95 mole% of the residues of diethylene glycol.
The sulfopolyesters of the instant invention are readily prepared from the appropriate dicarboxylic acids, esters, anhydrides, or salts, sulfomonomer, and the appropriate diol or diol mixtures using typical polycondensation reaction conditions. They may be made by continuous, semi-continuous, and batch modes of operation and may utilize a variety of reactor types. Examples of suitable reactor types include, but are not limited to, stirred tank, continuous stirred tank, slurry, tubular, wiped-film, falling film, or extrusion reactors. The term "continuous" as used herein means a process wherein reactants are introduced and products withdrawn simultaneously in an uninterrupted manner. By "continuous" it is meant that the process is substantially or completely continuous in operation and is to be contrasted with a "batch" process. "Continuous" is not meant in any way to prohibit normal interruptions in the continuity of the process due to, for example, start-up, reactor maintenance, or scheduled shut down periods. The term "batch" process as used herein means a process wherein all the reactants are added to the reactor and then processed according to a predetermined course of reaction during which no material is fed or removed into the reactor. The term "semicontinuous" means a process where some of the reactants are charged at the beginning of the process and the remaining reactants are fed continuously as the reaction progresses. Alternatively, a semicontinuous process may also include a process similar to a batch process in which all the reactants are added at the beginning of the process except that one or more of the products are removed continuously as the reaction progresses. The process is operated advantageously as a continuous process for economic reasons and to produce superior coloration of the polymer as the sulfopolyester may deteriorate in appearance if allowed to reside in a reactor at an elevated temperature for too long a duration.
The sulfopolyesters of the present invention are prepared by procedures known to persons skilled in the art. The sulfomonomer is most often added directly to the reaction mixture from which the polymer is made, although other processes are known and may also be employed, for example, as described in U. S. Patent No.'s 3,018,272, 3,075,952, and 3,033,822. The reaction of the sulfomonomer, diol component and the dicarboxylic acid component may be carried out using conventional polyester polymerization conditions. For example, when preparing the sulfopolyesters by means of an ester interchange reaction, i.e., from the ester form of the dicarboxylic acid components, the reaction process may comprise two steps. In the first step, the diol component and the dicarboxylic acid component, such as, for example, dimethyl isophthalate, are reacted at elevated temperatures, typically, about 15O0C to about 25O0C for about 0.5 to about 8 hours at pressures ranging from about 0.0 kPa gauge to about 414 kPa gauge (60 pounds per square inch, "psig"). Preferably, the temperature for the ester interchange reaction ranges from about 18O0C to about 23O0C for about 1 to about 4 hours while the preferred pressure ranges from about 103 kPa gauge (15 psig) to about 276 kPa gauge (40 psig). Thereafter, the reaction product is heated under higher temperatures and under reduced pressure to form sulfopolyester with the elimination of diol, which is readily volatilized under these conditions and removed from the system. This second step, or polycondensation step, is continued under higher vacuum and a temperature which generally ranges from about 23O0C. to about 35O0C, preferably about 25O0C to about 31O0C and most preferably about 26O0C to about 29O0C for about 0.1 to about 6 hours, or preferably, for about 0.2 to about 2 hours, until a polymer having the desired degree of polymerization, as determined by inherent viscosity, is obtained. The polycondensation step may be conducted under reduced pressure which ranges from about 53 kPa (400 torr) to about 0.013 kPa (0.1 torr). Stirring or appropriate conditions are used in both stages to ensure adequate heat transfer and surface renewal of the reaction mixture. The reactions of both stages are facilitated by appropriate catalysts such as, for example, alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyl tin compounds, metal oxides, and the like. A three-stage manufacturing procedure, similar to that described in U.S. Patent No. 5,290,631 , may also be used, particularly when a mixed monomer feed of acids and esters is employed. To ensure that the reaction of the diol component and dicarboxylic acid component by an ester interchange reaction mechanism is driven to completion, it is preferred to employ about 1.05 to about 2.5 moles of diol component to one mole dicarboxylic acid component. Persons of skill in the art will understand, however, that the ratio of diol component to dicarboxylic acid component is generally determined by the design of the reactor in which the reaction process occurs.
In the preparation of sulfopolyester by direct esterification, i.e., from the acid form of the dicarboxylic acid component, sulfopolyesters are produced by reacting the dicarboxylic acid or a mixture of dicarboxylic acids with the diol component or a mixture of diol components. The reaction is conducted at a pressure of from about 7 kPa gauge (1 psig) to about 1379 kPa gauge (200 psig), preferably less than 689 kPa (100 psig) to produce a low molecular weight, linear or branched sulfopolyester product having an average degree of polymerization of from about 1.4 to about 10. The temperatures employed during the direct esterification reaction typically range from about 18O0C to about 28O0C, more preferably ranging from about 22O0C to about 27O0C. This low molecular weight polymer may then be polymerized by a polycondensation reaction.
The water dispersible and multicomponent fibers and fibrous articles of this invention also may contain other conventional additives and ingredients which do not deleteriously affect their end use. For example, additives such as fillers, surface friction modifiers, light and heat stabilizers, extrusion aids, antistatic agents, colorants, dyes, pigments, fluorescent brighteners, antimicrobials, anticounterfeiting markers, hydrophobic and hydrophilic enhancers, viscosity modifiers, slip agents, tougheners, adhesion promoters, and the like may be used.
The fibers and fibrous articles of our invention do not require the presence of additives such as, for example, pigments, fillers, oils, waxes, or fatty acid finishes, to prevent blocking or fusing of the fibers during processing. The terms "blocking or fusing", as used herein, is understood to mean that the fibers or fibrous articles stick together or fuse into a mass such that the fiber cannot be processed or used for its intended purpose. Blocking and fusing can occur during processing of the fiber or fibrous article or during storage over a period of days or weeks and is exacerbated under hot, humid conditions.
In one embodiment of the invention, the fibers and fibrous articles will contain less than 10 wt% of such anti-blocking additives, based on the total weight of the fiber or fibrous article. For example, the fibers and fibrous articles may contain less than 10 wt% of a pigment or filler. In other examples, the fibers and fibrous articles may contain less than 9 wt%, less than 5 wt%, less than 3 wt%, less than 1 wt%, and 0 wt% of a pigment or filler, based on the total weight of the fiber. Colorants, sometimes referred to as toners, may be added to impart a desired neutral hue and/or brightness to the sulfopolyester. When colored fibers are desired, pigments or colorants may be included in the sulfopolyester reaction mixture during the reaction of the diol monomer and the dicarboxylic acid monomer or they may be melt blended with the preformed sulfopolyester. A preferred method of including colorants is to use a colorant having thermally stable organic colored compounds having reactive groups such that the colorant is copolymerized and incorporated into the sulfopolyester to improve its hue. For example, colorants such as dyes possessing reactive hydroxyl and/or carboxyl groups, including, but not limited to, blue and red substituted anthraquinones, may be copolymerized into the polymer chain. When dyes are employed as colorants, they may be added to the copolyester reaction process after an ester interchange or direct esterification reaction.
For the purposes of this invention, the term "fiber" refers to a polymeric body of high aspect ratio capable of being formed into two or three dimensional articles such as woven or nonwoven fabrics. In the context of the present invention, the term "fiber" is synonymous with "fibers" and intended to mean one or more fibers. The fibers of our invention may be unicomponent fibers, bicomponent, or multicomponent fibers. The term "unicomponent fiber", as used herein, is intended to mean a fiber prepared by melt spinning a single sulfopolyester, blends of one or more sulfopolyesters, or blends of one or more sulfopolyesters with one or more additional polymers and includes staple, monofilament, and multifilament fibers. "Unicomponent" is intended to be synonymous with the term "monocomponent" and includes "biconstituent" or "multiconstituent" fibers, and refers to fibers which have been formed from at least two polymers extruded from the same extruder as a blend. Unicomponent or biconstituent fibers do not have the various polymer components arranged in relatively constantly positioned distinct zones across the cross-sectional area of the fiber and the various polymers are usually not continuous along the entire length of the fiber, instead usually forming fibrils or protofibrils which start and end at random. Thus, the term "unicomponent" is not intended to exclude fibers formed from a polymer or blends of one or more polymers to which small amounts of additives may be added for coloration, anti-static properties, lubrication, hydrophilicity, etc.
By contrast, the term "multicomponent fiber", as used herein, intended to mean a fiber prepared by melting the two or more fiber forming polymers in separate extruders and by directing the resulting multiple polymer flows into one spinneret with a plurality of distribution flow paths but spun together to form one fiber. Multicomponent fibers are also sometimes referred to as conjugate or bicomponent fibers. The polymers are arranged in substantially constantly positioned distinct segments or zones across the cross-section of the conjugate fibers and extend continuously along the length of the conjugate fibers. The configuration of such a multicomponent fiber may be, for example, a sheath/core arrangement wherein one polymer is surrounded by another or may be a side by side arrangement, a pie arrangement or an "islands-in-the-sea" arrangement. For example, a multicomponent fiber may be prepared by extruding the sulfopolyester and one or more water non- dispersible polymers separately through a spinneret having a shaped or engineered transverse geometry such as, for example, an "islands-in-the-sea" or segmented pie configuration. Multicomponent fibers, typically, are staple, monofilament or multifilament fibers that have a shaped or round cross-section. Most fiber forms are heatset. The fiber may include the various antioxidants, pigments, and additives as described herein.
Monofilament fibers generally range in size from about 15 to about 8000 denier per filament (abbreviated herein as "d/f ')■ Our novel fibers typically will have d/f values in the range of about 40 to about 5000. Monofilaments may be in the form of unicomponent or multicomponent fibers. The multifilament fibers of our invention will preferably range in size from about 1.5 micrometers for melt blown webs, about 0.5 to about 50 d/f for staple fibers, and up to about 5000 d/f for monofilament fibers. Multifilament fibers may also be used as crimped or uncrimped yarns and tows. Fibers used in melt blown web and melt spun fabrics may be produced in microdenier sizes. The term "microdenier", as used herein, is intended to mean a d/f value of 1 d/f or less. For example, the microdenier fibers of the instant invention typically have d/f values of 1 or less, 0.5 or less, or 0.1 or less. Nanofibers can also be produced by electrostatic spinning.
As noted hereinabove, the sulfopolyesters also are advantageous for the preparation of bicomponent and multicomponent fibers having a shaped cross section. We have discovered that sulfopolyesters or blends of sulfopolyesters having a glass transition temperature (Tg) of at least 570C are particularly useful for multicomponent fibers to prevent blocking and fusing of the fiber during spinning and take up. Thus, our invention provides a multicomponent fiber having shaped cross section, comprising:
(A) a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 57°C, the sulfopolyester comprising:
(i) residues of one or more dicarboxylic acids;
(ii) about 4 to about 40 mole%, based on the total repeating units, of residues of at least one sulfomonomer having 2 functional groups and one or more sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
(iii) one or more diol residues wherein at least 25 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2VOH wherein n is an integer in the range of 2 to about 500; and
(iv) 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof; and (B) a plurality of segments comprising one or more water non-dispersible polymers immiscible with the sulfopolyester, wherein the segments are substantially isolated from each other by the sulfopolyester intervening between the segments; wherein the fiber has an islands-in-the-sea or segmented pie cross section and contains less than 10 weight percent of a pigment or filler, based on the total weight of the fiber.
The dicarboxylic acids, diols, sulfopolyester, sulfomonomers, and branching monomers residues are as described previously for other embodiments of the invention. For multicomponent fibers, it is advantageous that the sulfopolyester have a Tg of at least 570C. Further examples of glass transition temperatures that may be exhibited by the sulfopolyester or sulfopolyester blend of our multicomponent fiber are at least 6O0C, at least 650C, at least 7O0C, at least 750C, at least 8O0C, at least 850C, and at least 9O0C. Further, to obtain a sulfopolyester with a Tg of at least 570C, blends of one or more sulfopolyesters may be used in varying proportions to obtain a sulfopolyester blend having the desired Tg. The Tg of a sulfopolyester blend may be calculated by using a weighted average of the Tg' s of the sulfopolyester components. For example, sulfopolyester having a Tg of 480C may be blended in a 25:75 wt:wt ratio with another sulfopolyester having Tg of 650C to give a sulfopolyester blend having a Tg of approximately 610C.
In another embodiment of the invention, the water dispersible sulfopolyester component of the multicomponent fiber presents properties which allow at least one of the following:
(A) the multicomponent fibers to be spun to a desired low denier,
(B) the sulfopolyester in these mulficomponent fibers is resistant to removal during hydroentangling of a web formed from the fibers but is efficiently removed at elevated temperatures after hydroentanglement, and
(C) the multicomponent fibers are heat settable to yield a stable, strong fabric. Surprising and unexpected results were achieved in furtherance of these objectives using a sulfopolyester having a certain melt viscosity and level of sulfomonomer residues.
Therefore, in this embodiment of the invention, a multicomponent fiber is provided having a shaped cross section comprising:
(A) at least one water dispersible sulfopolyester; and
(B) a plurality of domains comprising one or more water non-dispersible polymers immiscible with the sulfopolyester, wherein said domains are substantially isolated from each other by the sulfopolyester intervening between the domains, wherein the fiber has an as-spun denier of less than about 6 denier per filament; wherein the water dispersible sulfopolyesters exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprises less than about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residues.
The sulfopolyester utilized in these multicomponent fibers has a melt viscosity of generally less than about 12,000 poise. Preferably, the melt viscosity of the sulfopolyester is less than 10,000 poise, more preferably, less than 6,000, and most preferably, less than 4,000 poise measured at 240°C and 1 rad/sec shear rate. In another aspect, the sulfopolyester exhibits a melt viscosity of between about 1000- 12000 poise, more preferably between 2000-6000 poise, and most preferably between 2500-4000 poise measured at 2400C and 1 rad/sec shear rate. Prior to determining the viscosity, the samples are dried at 600C in a vacuum oven for 2 days. The melt viscosity is measured on rheometer using a 25 mm diameter parallel-plate geometry at lmm gap setting. A dynamic frequency sweep is run at a strain rate range of 1 to 400 rad/sec and 10% strain amplitude. The viscosity is then measured at 240° C and strain rate of 1 rad/sec.
The level of sulfomonomer residues in the sulfopolyester polymers for use in accordance with this aspect of the present invention is generally less than about 25 mole %, and preferably, less than 20 mole %, reported as a percentage of the total diacid or diol residues in the sulfopolyester. More preferably, this level is between about 4 to about 20 mole %, even more preferably between about 5 to about 12 mole %, and most preferably between about 7 to about 10 mole %. Sulfomonomers for use with the invention preferably have 2 functional groups and one or more sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof. A sodiosulfo-isophthalic acid monomer is particularly preferred.
In addition to the sulfomonomer described previously, the sulfopolyester preferably comprises residues of one or more dicarboxylic acids, one or more diol residues wherein at least 25 mole %, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CHa)n-OH wherein n is an integer in the range of 2 to about 500, and 0 to about 20 mole %, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof.
In a particularly preferred embodiment, the sulfopolyester comprises from about 80-96 mole % dicarboxylic acid residues, from about 4 to about 20 mole % sulfomonomer residues, and 100 mole % diol residues (there being a total mole % of 200%, i.e., 100 mole % diacid and 100 mole % diol). More specifically, the dicarboxylic portion of the sulfopolyester comprises between about 60-80 mole % terephthalic acid, about 0-30 mole % isophthalic acid, and about 4-20 mole % 5- sodiosulfoisophthalic acid (5-SSIPA). The diol portion comprises from about 0-50 mole % diethylene glycol and from about 50-100 mole % ethylene glycol. An exemplary formulation according to this embodiment of the invention is set forth subsequently.
Figure imgf000039_0001
Figure imgf000040_0001
The water non-dispersible component of the multicomponent fiber may comprise any of those water non-dispersible polymers described herein. Spinning of the fiber may also occur according to any method described herein. However, the improved rheological properties of multicomponent fibers in accordance with this aspect of the invention provide for enhanced drawings speeds. When the sulfopolyester and water non-dispersible polymer are extruded to produce multicomponent extrudates, the multicomponent extrudate is capable of being melt drawn to produce the multicomponent fiber, using any of the methods disclosed herein, at a speed of at least about 2000 m/min, more preferably at least about 3000 m/min, even more preferably at least about 4000 m/min, and most preferably at least about 4500 m/min. Although not intending to be bound by theory, melt drawing of the multicomponent extrudates at these speeds results in at least some oriented crystallinity in the water non-dispersible component of the multicomponent fiber. This oriented crystallinity can increase the dimensional stability of non- woven materials made from the multicomponent fibers during subsequent processing.
Another advantage of the multicomponent extrudate is that it can be melt drawn to a multicomponent fiber having an as-spun denier of less than 6 deniers per filament. Other ranges of multicomponent fiber sizes include an as-spun denier of less than 4 deniers per filament and less than 2.5 deniers per filament.
Therefore, in another embodiment of the invention, a multicomponent extrudate having a shaped cross section, comprising:
(A) at least one water dispersible sulfopolyester; and
(B) a plurality of domains comprising one or more water non-dispersible polymers immiscible with the sulfopolyester, wherein the domains are substantially isolated from each other by the sulfopolyester intervening between the domains, wherein the extrudate is capable of being melt drawn at a speed of at least about 2000 m/min.
The multicomponent fiber comprises a plurality of segments or domains of one or more water non-dispersible polymers immiscible with the sulfopolyester in which the segments or domains are substantially isolated from each other by the sulfopolyester intervening between the segments or domains. The term "substantially isolated", as used herein, is intended to mean that the segments or domains are set apart from each other to permit the segments domains to form individual fibers upon removal of the sulfopolyester. For example, the segments or domains may be touching each others as in, for example, a segmented pie configuration but can be split apart by impact or when the sulfopolyester is removed.
The ratio by weight of the sulfopolyester to water non-dispersible polymer component in the multicomponent fiber of the invention is generally in the range of about 60:40 to about 2:98 or, in another example, in the range of about 50:50 to about 5:95. Typically, the sulfopolyester comprises 50% by weight or less of the total weight of the multicomponent fiber.
The segments or domains of multicomponent fiber may comprise one of more water non-dispersible polymers. Examples of water non-dispersible polymers which may be used in segments of the multicomponent fiber include, but are not limited to, polyolefins, polyesters, polyamides, polylactides, polycaprolactone, polycarbonate, polyurethane, cellulose ester, and polyvinyl chloride. For example, the water non- dispersible polymer may be polyester such as poly(ethylene) terephthalate, poly(butylene) terephthalate, poly(cyclohexylene) cyclohexanedicarboxylate, poly(cyclohexylene) terephthalate, poly(trimethylene) terephthalate, and the like. In another example, the water non-dispersible polymer can be biodistintegratable as determined by DIN Standard 54900 and/or biodegradable as determined by ASTM Standard Method, D6340-98. Examples of biodegradable polyesters and polyester blends are disclosed in U.S. Patent No.'s 5,599,858; 5,580,91 1 ; 5,446,079; and 5,559,171. The term "biodegradable", as used herein in reference to the water non- dispersible polymers of the present invention, is understood to mean that the polymers are degraded under environmental influences such as, for example, in a composting environment, in an appropriate and demonstrable time span as defined, for example, by ASTM Standard Method, D6340-98, entitled "Standard Test Methods for Determining Aerobic Biodegradation of Radiolabeled Plastic Materials in an Aqueous or Compost Environment". The water non-dispersible polymers of the present invention also may be "biodisintegratable", meaning that the polymers are easily fragmented in a composting environment as defined, for example, by DIN Standard 54900. For example, the biodegradable polymer is initially reduced in molecular weight in the environment by the action of heat, water, air, microbes and other factors. This reduction in molecular weight results in a loss of physical properties (tenacity) and often in fiber breakage. Once the molecular weight of the polymer is sufficiently low, the monomers and oligomers are then assimilated by the microbes. In an aerobic environment, these monomers or oligomers are ultimately oxidized to CO2, H2O, and new cell biomass. In an anaerobic environment, the monomers or oligomers are ultimately converted to CO2, H2, acetate, methane, and cell biomass.
For example, water non-dispersible polymer may be an aliphatic-aromatic polyester, abbreviated herein as "AAPE". The term "aliphatic-aromatic polyester", as used herein, means a polyester comprising a mixture of residues from aliphatic or cycloaliphatic dicarboxylic acids or diols and aromatic dicarboxylic acids or diols. The term "non-aromatic", as used herein with respect to the dicarboxylic acid and diol monomers of the present invention, means that carboxyl or hydroxyl groups of the monomer are not connected through an aromatic nucleus. For example, adipic acid contains no aromatic nucleus in its backbone, i.e., the chain of carbon atoms connecting the carboxylic acid groups, thus is "non-aromatic". By contrast, the term "aromatic" means the dicarboxylic acid or diol contains an aromatic nucleus in the backbone such as, for example, terephthalic acid or 2,6-naphthalene dicarboxylic acid. "Non-aromatic", therefore, is intended to include both aliphatic and cycloaliphatic structures such as, for example, diols and dicarboxylic acids, which contain as a backbone a straight or branched chain or cyclic arrangement of the constituent carbon atoms which may be saturated or paraffinic in nature, unsaturated, i.e., containing non-aromatic carbon-carbon double bonds, or acetylenic, i.e., containing carbon- carbon triple bonds. Thus, in the context of the description and the claims of the present invention, non-aromatic is intended to include linear and branched, chain structures (referred to herein as "aliphatic") and cyclic structures (referred to herein as "alicyclic" or "cycloaliphatic"). The term "non-aromatic", however, is not intended to exclude any aromatic substituents which may be attached to the backbone of an aliphatic or cycloaliphatic diol or dicarboxylic acid. In the present invention, the difunctional carboxylic acid typically is a aliphatic dicarboxylic acid such as, for example, adipic acid, or an aromatic dicarboxylic acid such as, for example, terephthalic acid. The difunctional hydroxyl compound may be cycloaliphatic diol such as, for example, 1,4-cyclohexanedimethanol, a linear or branched aliphatic diol such as, for example, 1 ,4-butanediol, or an aromatic diol such as, for example, hydroquinone.
The AAPE may be a linear or branched random copolyester and/or chain extended copolyester comprising diol residues which comprise the residues of one or more substituted or unsubstituted, linear or branched, diols selected from aliphatic diols containing 2 to about 8 carbon atoms, polyalkylene ether glycols containing 2 to 8 carbon atoms, and cycloaliphatic diols containing about 4 to about 12 carbon atoms. The substituted diols, typically, will comprise 1 to about 4 substituents independently selected from halo, C6-Ci0 aryl, and C1-C4 alkoxy. Examples of diols which may be used include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethyl-l,3-propanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol, diethylene glycol, 2,2,4- trimethyl-l,6-hexanediol, thiodiethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-l,3-cyclobutanediol, Methylene glycol, and tetraethylene glycol with the preferred diols comprising one or more diols selected from 1 ,4-butanediol; 1,3-propanediol; ethylene glycol; 1,6-hexanediol; diethylene glycol; or 1,4-cyclohexanedimethanol. The AAPE also comprises diacid residues which contain about 35 to about 99 mole%, based on the total moles of diacid residues, of the residues of one or more substituted or unsubstituted, linear or branched, non-aromatic dicarboxylic acids selected from aliphatic dicarboxylic acids containing 2 to about 12 carbon atoms and cycloaliphatic acids containing about 5 to about 10 carbon atoms. The substituted non-aromatic dicarboxylic acids will typically contain 1 to about 4 substituents selected from halo, C6-C10 aryl, and Ci-C4 alkoxy. Non-limiting examples of non-aromatic diacids include malonic, succinic, glutaric, adipic, pimelic, azelaic, sebacic, fumaric, 2,2-dimethyl glutaric, suberic, 1,3- cyclopentanedicarboxylic, 1,4-cyclohexanedicarboxylic, 1,3- cyclohexanedicarboxylic, diglycolic, itaconic, maleic, and 2,5-norbornane- dicarboxylic. In addition to the non-aromatic dicarboxylic acids, the AAPE comprises about 1 to about 65 mole%, based on the total moles of diacid residues, of the residues of one or more substituted or unsubstituted aromatic dicarboxylic acids containing 6 to about 10 carbon atoms. In the case where substituted aromatic dicarboxylic acids are used, they will typically contain 1 to about 4 substituents selected from halo, C6-CI0 aryl, and Ci-C4 alkoxy. Non-limiting examples of aromatic dicarboxylic acids which may be used in the AAPE of our invention are terephthalic acid, isophthalic acid, salts of 5-sulfoisophthalic acid, and 2,6- naphthalenedicarboxylic acid. More preferably, the non-aromatic dicarboxylic acid will comprise adipic acid, the aromatic dicarboxylic acid will comprise terephthalic acid, and the diol will comprise 1,4-butanediol.
Other possible compositions for the AAPE' s of our invention are those prepared from the following diols and dicarboxylic acids (or polyester-forming equivalents thereof such as diesters) in the following mole percentages, based on 100 mole percent of a diacid component and 100 mole percent of a diol component:
(1) glutaric acid (about 30 to about 75%); terephthalic acid (about 25 to about 70%); 1,4-butanediol (about 90 to 100%); and modifying diol (0 about 10%);
(2) succinic acid (about 30 to about 95%); terephthalic acid (about 5 to about 70%); 1,4-butanediol (about 90 to 100%); and modifying diol (0 to about 10%); and
(3) adipic acid (about 30 to about 75%); terephthalic acid (about 25 to about 70%); 1,4-butanediol (about 90 to 100%); and modifying diol (0 to about 10%).
The modifying diol preferably is selected from 1 ,4-cyclohexanedimethanol, triethylene glycol, polyethylene glycol and neopentyl glycol. The most preferred AAPE's are linear, branched or chain extended copolyesters comprising about 50 to about 60 mole percent adipic acid residues, about 40 to about 50 mole percent terephthalic acid residues, and at least 95 mole percent 1 ,4-butanediol residues. Even more preferably, the adipic acid residues comprise about 55 to about 60 mole percent, the terephthalic acid residues comprise about 40 to about 45 mole percent, and the diol residues comprise about 95 mole percent 1 ,4-butanediol residues. Such compositions are commercially available under the trademark EASTAR BIO® copolyester from Eastman Chemical Company, Kingsport, TN, and under the trademark ECOFLEX from BASF Corporation.
Additional, specific examples of preferred AAPE's include a poly(tetra- methylene glutarate-co-terephthalate) containing (a) 50 mole percent glutaric acid residues, 50 mole percent terephthalic acid residues, and 100 mole percent 1,4- butanediol residues, (b) 60 mole percent glutaric acid residues, 40 mole percent terephthalic acid residues, andlOO mole percent 1 ,4-butanediol residues or (c) 40 mole percent glutaric acid residues, 60 mole percent terephthalic acid residues, and 100 mole percent 1 ,4-butanediol residues; a poly(tetramethylene succinate-co- terephthalate) containing (a) 85 mole percent succinic acid residues, 15 mole percent terephthalic acid residues, and 100 mole percent 1 ,4-butanediol residues or (b) 70 mole percent succinic acid residues, 30 mole percent terephthalic acid residues, and 100 mole percent 1 ,4-butanediol residues; a poly(ethylene succinate-co-terephthalate) containing 70 mole percent succinic acid residues, 30 mole percent terephthalic acid residues, and 100 mole percent ethylene glycol residues; and a poly(tetramethylene adipate-co-terephthalate) containing (a) 85 mole percent adipic acid residues, 15 mole percent terephthalic acid residues, and 100 mole percent 1 ,4-butanediol residues; or (b) 55 mole percent adipic acid residues, 45 mole percent terephthalic acid residues, and 100 mole percent 1 ,4-butanediol residues.
The AAPE preferably comprises from about 10 to about 1,000 repeating units and preferably, from about 15 to about 600 repeating units. The AAPE may have an inherent viscosity of about 0.4 to about 2.0 dL/g, or more preferably about 0.7 to about 1.6 dL/g, as measured at a temperature of 25°C using a concentration of 0.5 gram copoly ester in 100 ml of a 60/40 by weight solution of phenol/tetrachloroethane.
The AAPE, optionally, may contain the residues of a branching agent. The mole percentage ranges for the branching agent are from about 0 to about 2 mole%, preferably about 0.1 to about 1 mole%, and most preferably about 0.1 to about 0.5 mole% based on the total moles of diacid or diol residues (depending on whether the branching agent contains carboxyl or hydroxyl groups). The branching agent preferably has a weight average molecular weight of about 50 to about 5000, more preferably about 92 to about 3000, and a functionality of about 3 to about 6. The branching agent, for example, may be the esterified residue of a polyol having 3 to 6 hydroxyl groups, a polycarboxylic acid having 3 or 4 carboxyl groups (or ester- forming equivalent groups) or a hydroxy acid having a total of 3 to 6 hydroxyl and carboxyl groups. In addition, the AAPE may be branched by the addition of a peroxide during reactive extrusion.
Each segment of the water non-dispersible polymer may be different from others in fineness and may be arranged in any shaped or engineered cross-sectional geometry known to persons skilled in the art. For example, the sulfopolyester and a water non-dispersible polymer may be used to prepare a bicomponent fiber having an engineered geometry such as, for example, a side-by-side, "islands-in-the-sea", segmented pie, other splitables, sheath/core, or other configurations known to persons skilled in the art. Other multicomponent configurations are also possible. Subsequent removal of a side, the "sea", or a portion of the "pie" can result in very fine fibers. The process of preparing bicomponent fibers also is well known to persons skilled in the art. In a bicomponent fiber, the sulfopolyester fibers of this invention may be present in amounts of about 10 to about 90 weight% and will generally be used in the sheath portion of sheath/core fibers. Typically, when a water-insoluble or water non- dispersible polymer is used, the resulting bicomponent or multicomponent fiber is not completely water-dispersible. Side by side combinations with significant differences in thermal shrinkage can be utilized for the development of a spiral crimp. If crimping is desired, a saw tooth or stuffer box crimp is generally suitable for many applications. If the second polymer component is in the core of a sheath/core configuration, such a core optionally may be stabilized.
The sulfopolyesters are particularly useful for fibers having an "islands-in-the- sea" or "segmented pie" cross section as they only requires neutral or slightly acidic (i.e., "soft" water) to disperse, as compared to the caustic-containing solutions that are sometimes required to remove other water dispersible polymers from multicomponent fibers. The term "soft water" as used in this disclosure means that the water has up to 5 grains per gallon as CaCO3 (1 grain of CaCO3 per gallon is equivalent to 17.1 ppm). Thus another aspect of our invention is a multicomponent fiber, comprising:
(A) a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 570C, the sulfopolyester comprising:
(i) about 50 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid, based on the total acid residues;
(ii) about 4 to about 30 mole%, based on the total acid residues, of a residue of sodiosulfoisophthalic acid;
(iii) one or more diol residues wherein at least 25 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500;
(iv) 0 to about 20 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof; and
(B) a plurality of segments comprising one or more water non-dispersible polymers immiscible with the sulfopolyester, wherein the segments are substantially isolated from each other by the sulfopolyester intervening between the segments; wherein the fiber has an islands-in-the-sea or segmented pie cross section and contains less than 10 weight percent of a pigment or filler, based on the total weight of the fiber.
The dicarboxylic acids, diols, sulfopolyester, sulfomonomers, branching monomers residues, and water non-dispersible polymers are as described previously. For multicomponent fibers, it is advantageous that sulfopolyester have a Tg of at least 570C. The sulfopolyester may be a single sulfopolyester or a blend of one or more sulfopolyester polymers. Further examples of glass transition temperatures that may be exhibited by the sulfopolyester or sulfopolyester blends are at least 650C, at least 7O0C, at least 750C, at least 850C, and at least 9O0C. For example, the sulfopolyester may comprise about 75 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid and about 25 to about 95 mole% of a residue of diethylene glycol. As described hereinabove, examples of the water non-dispersible polymers are polyolefins, polyesters, polyamides, polylactides, polycaprolactones, polycarbonates, polyurethanes, cellulose esters, and polyvinyl chlorides. In addition, the water non- dispersible polymer may be biodegradable or biodisintegratable. For example, the water non-dispersible polymer may be an aliphatic-aromatic polyester as described previously.
Our novel multicomponent fiber may be prepared by any number of methods known to persons skilled in the art. The present invention thus provides a process for a multicomponent fiber having a shaped cross section comprising: spinning a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 570C and one or more water non-dispersible polymers immiscible with the sulfopolyester into a fiber, the sulfopolyester comprising:
(i) residues of one or more dicarboxylic acids;
(ii) about 4 to about 40 mole%, based on the total repeating units, of residues of at least one sulfomonomer having 2 functional groups and one or more sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
(iii) one or more diol residues wherein at least 25 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500; and
(iv) 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof; wherein the fiber has a plurality of segments comprising the water non- dispersible polymers and the segments are substantially isolated from each other by the sulfopolyester intervening between the segments and the fiber contains less than 10 weight percent of a pigment or filler, based on the total weight of the fiber. For example, the multicomponent fiber may be prepared by melting the sulfopolyester and one or more water non-dispersible polymers in separate extruders and directing the individual polymer flows into one spinneret or extrusion die with a plurality of distribution flow paths such that the water non-dispersible polymer component form small segments or thin strands which are substantially isolated from each other by the intervening sulfopolyester. The cross section of such a fiber may be, for example, a segmented pie arrangement or an islands-in-the-sea arrangement. In another example, the sulfopolyester and one or more water non-dispersible polymers are separately fed to the spinneret orifices and then extruded in sheath-core form in which the water non-dispersible polymer forms a "core" that is substantially enclosed by the sulfopolyester "sheath" polymer. In the case of such concentric fibers, the orifice supplying the "core" polymer is in the center of the spinning orifice outlet and flow conditions of core polymer fluid are strictly controlled to maintain the concentricity of both components when spinning. Modifications in spinneret orifices enable different shapes of core and/or sheath to be obtained within the fiber cross- section. In yet another example, a multicomponent fiber having a side-by-side cross section or configuration may be produced by coextruding the water dispersible sulfopolyester and water non-dispersible polymer through orifices separately and converging the separate polymer streams at substantially the same speed to merge side-by-side as a combined stream below the face of the spinneret; or (2) by feeding the two polymer streams separately through orifices, which converge at the surface of the spinneret, at substantially the same speed to merge side-by-side as a combined stream at the surface of the spinneret. In both cases, the velocity of each polymer stream, at the point of merge, is determined by its metering pump speed, the number of orifices, and the size of the orifice. The dicarboxylic acids, diols, sulfopolyester, sulfomonomers, branching monomers residues, and water non-dispersible polymers are as described previously. The sulfopolyester has a glass transition temperature of at least 570C. Further examples of glass transition temperatures that may be exhibited by the sulfopolyester or sulfopolyester blend are at least 650C, at least 7O0C, at least 750C, at least 850C, and at least 9O0C. In one example, the sulfopolyester may comprise about 50 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid, based on the total acid residues; and about 4 to about 30 mole%, based on the total acid residues, of a residue of sodiosulfoisophthalic acid; and 0 to about 20 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof. In another example, the sulfopolyester may comprise about 75 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid and about 25 to about 95 mole% of a residue of diethylene glycol. As described hereinabove, examples of the water non-dispersible polymers are polyolefins, polyesters, polyamides, polylactides, polycaprolactone, polycarbonate, polyurethane, and polyvinyl chloride. In addition, the water non-dispersible polymer may be biodegradable or biodisintegratable. For example, the water non-dispersible polymer may be an aliphatic-aromatic polyester as described previously. Examples of shaped cross sections include, but are not limited to, islands-in-the-sea, side-by-side, sheath- core, or segmented pie configurations.
In another embodiment of the invention, a process for making a multicomponent fiber having a shaped cross section is provided comprising: spinning at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with the sulfopolyester to produce a multicomponent fiber, wherein the multicomponent fiber has a plurality of domains comprising the water non-dispersible polymers and the domains are substantially isolated from each other by the sulfopolyester intervening between the domains; wherein the water dispersible sulfopolyester exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprising less than about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residues; and wherein the multicomponent fiber has an as-spun denier of less than about 6 denier per filament.
The sulfopolyester utilized in these multicomponent fiber and the water non- dispersible polymers were discussed previously in this disclosure.
In another embodiment of this invention, a process for making a multicomponent fiber having a shaped cross section is provided comprising:
(A) extruding at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with said sulfopolyester to produce a multicomponent extrudate, wherein the multicomponent extrudate has a plurality of domains comprising the water non-dispersible polymers and the domains are substantially isolated from each other by the sulfopolyester intervening between the domains; and
(B) melt drawing the multicomponent extrudate at a speed of at least about 2000 m/min to produce the multicomponent fiber.
It is also a feature of this embodiment of the invention that the process includes the step of melt drawing the multicomponent extrudate at a speed of at least about 2000 m/min, more preferably, at least about 3000 m/min, and most preferably at least 4500 m/min.
Typically, upon exiting the spinneret, the fibers are quenched with a cross flow of air whereupon the fibers solidify. Various finishes and sizes may be applied to the fiber at this stage. The cooled fibers, typically, are subsequently drawn and wound up on a take up spool. Other additives may be incorporated in the finish in effective amounts like emulsifiers, antistatics, antimicrobials, antifoams, lubricants, thermostabilizers, UV stabilizers, and the like.
Optionally, the drawn fibers may be textured and wound-up to form a bulky continuous filament. This one-step technique is known in the art as spin-draw- texturing. Other embodiments include flat filament (non-textured) yarns, or cut staple fiber, either crimped or uncrimped.
The sulfopolyester may be later removed by dissolving the interfacial layers or pie segments and leaving the smaller filaments or microdenier fibers of the water non- dispersible polymer(s). Our invention thus provides a process for microdenier fibers comprising:
(A) spinning a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 570C and one or more water non-dispersible polymers immiscible with the sulfopolyester into multicomponent fibers, the sulfopolyester comprising:
(i) about 50 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid, based on the total acid residues;
(ii) about 4 to about 30 mole%, based on the total acid residues, of a residue of sodiosulfoisophthalic acid;
(iii) one or more diol residues wherein at least 25 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500; and
(iv) 0 to about 20 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof; wherein the fibers have a plurality of segments comprising the water non- dispersible polymers wherein the segments are substantially isolated from each other by the sulfopolyester intervening between the segments and the fibers contain less than 10 weight percent of a pigment or filler, based on the total weight of the fibers; and
(B) contacting the multicomponent fibers with water to remove the sulfopolyester thereby forming microdenier fibers.
Typically, the multicomponent fiber is contacted with water at a temperature of about 250C to about 1000C, preferably about 500C to about 8O0C for a time period of from about 10 to about 600 seconds whereby the sulfopolyester is dissipated or dissolved. After removal of the sulfopolyester, the remaining water non-dispersible polymer microfibers typically will have an average fineness of 1 d/f or less, typically, 0.5 d/f or less, or more typically, 0.1 d/f or less. Typical applications of these remaining water non-dispersible polymer microfibers include nonwoven fabrics, such as, for example, artificial leathers, suedes, wipes, and filter media. Filter media produce from these microfibers can be utilized to filter air or liquids. Filter media for liquids include, but are not limited to, water, bodily fluids, solvents, and hydrocarbons. The ionic nature of sulfopolyesters also results in advantageously poor "solubility" in saline media, such as body fluids. Such properties are desirable in personal care products and cleaning wipes that are flushable or otherwise disposed in sanitary sewage systems. Selected sulfopolyesters have also been utilized as dispersing agents in dye baths and soil redeposition preventative agents during laundry cycles.
In another embodiment of the present invention, a process for making microdenier fibers is provided comprising spinning at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with the water dispersible sulfopolyester into multicomponent fibers, wherein said multicomponent fibers have a plurality of domains comprising said water non- dispersible polymers wherein the domains are substantially isolated from each other by the sulfopolyester intervening between the domains; wherein the fiber has an as- spun denier of less than about 6 denier per filament; wherein the water dispersible sulfopolyester exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprising less than about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residues; and contacting the multicomponent fibers with water to remove the water dispersible sulfopolyester thereby forming microdenier fibers.
In another embodiment of the invention, a process for making microdenier fibers is provided comprising:
(A) extruding at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with said water dispersible sulfopolyester to produce multicomponent extrudates, wherein said multicomponent extrudates have a plurality of domains comprising said water non-dispersible polymers wherein said domains are substantially isolated from each other by said sulfopolyester intervening between said domains;
(B) melt drawing said multicomponent extrudates at a speed of at least about 2000 m/min to form multicomponent fibers; and
(C) contacting said multicomponent fibers with water to remove said water dispersible sulfopolyester thereby forming microdenier fibers.
It is preferable that the melt drawing of the multicomponent extrudates at a speed of at least about 2000 m/min, more preferably at least about 3000 m/min, and most preferably at least 4500 m/min.
Such sulfomonomers and sulfopolyesters suitable for use in accordance with the invention are described above.
As the preferred sulfopolyesters for use in accordance with this aspect of the invention are generally resistant to removal during subsequent hydroentangling processes, it is preferable that the water used to remove the sulfopolyester from the multicomponent fibers be above room temperature, more preferably the water is at least about 45 °C, even more preferably at least about 60°C, and most preferably at least about 80°C.
In another embodiment of this invention, another process is provided to produce water non-dispersible polymer microfibers. The process comprises: a) cutting a multicomponent fiber into cut multicomponent fibers; b) contacting a fiber-containing feedstock with water to produce a fiber mix slurry; wherein said fiber-containing feedstock comprises cut multicomponent fibers; c) heating said fiber mix slurry to produce a heated fiber mix slurry; d) optionally, mixing said fiber mix slurry in a shearing zone; e) removing at least a portion of the sulfopolyester from said multicomponent fiber to produce a slurry mixture comprising a sulfopolyester dispersion and the water non-dispersible polymer microfibers; and f) separating the water non-dispersible polymer microfibers from said slurry mixture. The multicomponent fiber can be cut into any length that can be utilized to produce nonwoven articles. In one embodiment of the invention, the multicomponent fiber is cut into lengths ranging from about lmm to about 50 mm. In another aspect of the invention, the multicomponent fiber can be cut into a mixture of different lengths.
The fiber-containing feedstock can comprise any other type of fiber that is useful in the production of nonwoven articles. In one embodiment, the fiber- containing feedstock further comprises at least one fiber selected from the group consisting of cellulosic fiber pulp, glass fiber, polyester fibers, nylon fibers, polyolefin fibers, rayon fibers and cellulose ester fibers.
The fiber-containing feedstock is mixed with water to produce a fiber mix slurry. Preferably, to facilitate the removal of the water-dispersible sulfopolyester, the water utilized can be soft water or deionized water. Soft water has been previously defined in this disclosure. In one embodiment of this invention, at least one water softening agent may be used to facilitate the removal of the water-dispersible sulfopolyester from the multicomponent fiber. Any water softening agent known in the art can be utilized. In one embodiment, the water softening agent is a chelating agent or calcium ion sequestrant. Applicable chelating agents or calcium ion sequestrants are compounds containing a plurality of carboxylic acid groups per molecule where the carboxylic groups in the molecular structure of the chelating agent are separated by 2 to 6 atoms. Tetrasodium ethylene diamine tetraacetic acid (EDTA) is an example of the most common chelating agent, containing four carboxylic acid moieties per molecular structure with a separation of 3 atoms between adjacent carboxylic acid groups. Poly acrylic acid, sodium salt is an example of a calcium sequestrant containing carboxylic acid groups separated by two atoms between carboxylic groups. Sodium salts of maleic acid or succinic acid are examples of the most basic chelating agent compounds. Further examples of applicable chelating agents include compounds which have in common the presence of multiple carboxylic acid groups in the molecular structure where the carboxylic acid groups are separated by the required distance (2 to 6 atom units) which yield a favorable steric interaction with di- or multi- valent cations such as calcium which cause the chelating agent to preferentially bind to di- or multi valent cations. Such compounds include, but are not limited to, diethylenetriaminepentaacetic acid; diethylenetriamine- N,N,N',N',N"-pentaacetic acid; pentetic acid; N,N-bis(2-(bis- (carboxymethyl)amino)ethyl)-glycine; diethylenetriamine pentaacetic acid; [[(carboxymethyl)imino]bis(ethylenenitrilo)]-tetra-acetic acid; edetic acid; ethylenedinitrilotetraacetic acid; EDTA, free base; EDTA free acid; ethylenediamine- N,N,N',N'-tetraacetic acid; hampene; versene; N3N'- 1 ,2-ethane diylbis-(N- (carboxymethyl)glycine); ethylenediamine tetra-acetic acid; N5N- bis(carboxymethyl)glycine; triglycollamic acid; trilone A; alpha,alpha',alpha"- trimethylaminetricarboxylic acid; tri(carboxymethyl)amine; aminotriacetic acid; hampshire NTA acid; nitrilo-2,2',2"-triacetic acid; titriplex i; nitrilotriacetic acid; and mixtures thereof.
The amount of water softening agent needed depends on the hardness of the water utilized in terms of Ca+* and other multivalent ions.
The fiber mix slurry is heated to produce a heated fiber mix slurry. The temperature is that which is sufficient to remove a portion of the sulfopolyester from the multicomponent fiber. In one embodiment of the invention, the fiber mix slurry is heated to a temperature ranging from about 50°C to about 100°C. Other temperature ranges are from about 70°C to about 100°C, about 80°C to about 100°C, and about 90°C to about 100°C.
Optionally, the fiber mix slurry is mixed in a shearing zone. The amount of mixing is that which is sufficient to disperse and remove a portion of the water dispersible sulfopolyester from the multicomponent fiber and separate the water non- dispersible polymer microfibers. In one embodiment of the invention, 90% of the sulfopolyester is removed. In another embodiment, 95% of the sulfopolyester is removed, and in yet another embodiment, 98% or greater of the sulfopolyester is removed. The shearing zone can comprise any type of equipment that can provide shearing action necessary to disperse and remove a portion of the water dispersible sulfopolyester from the multicomponent fiber and separate the water non-dispersible polymer microfibers. Examples of such equipment include, but is not limited to, pulpers and refiners.
The water dispersible sulfopolyester in the multicomponent fiber after contact with water and heating disperse and separate from the water non-dispersible polymer fiber to produce a slurry mixture comprising a sulfopolyester dispersion and the water non-dispersible polymer microfibers. The water non-dispersible polymer microfibers can then be separated from the sulfopolyester dispersion by any means known in the art. For examples, the slurry mixture can be routed through separating equipment, such as for example, screens and filters. Optionally, the water non-dispersible polymer microfibers may be washed once or numerous times to remove more of the water-dispersible sulfopolyester.
The removal of the water-dispersible sulfopolyester can be determined by physical observation of the slurry mixture. The water utilized to rinse the water non- dispersible polymer microfibers is clear if the water-dispersible sulfopolyester has been mostly removed. If the water-dispersible sulfopolyester is still being removed, the water utilized to rinse the water non-dispersible polymer microfibers can be milky. Further, if water-dispersible sulfopolyester remains on the water non- dispersible polymer microfibers, the microfibers can be somewhat sticky to the touch.
The water-dispersible sulfopolyester can be recovered from the sulfopolyester dispersion by any method known in the art.
In another embodiment of this invention, a water non-dispersible polymer microfiber is provided comprising at least one water non-dispersible polymer wherein the water non-dispersible polymer microfiber has an equivalent diameter of less than 5 microns and length of less than 25 millimeters. This water non-dispersible polymer microfiber is produced by the processes previously described to produce microfibers. In another aspect of the invention, the water non-dispersible polymer microfiber has an equivalent diameter of less than 3 microns and length of less than 25 millimeters. In other embodiments of the invention, the water non-dispersible polymer microfiber has an equivalent diameter of less than 5 microns or less than 3 microns. In other embodiments of the invention, the water non-dispersible polymer microfiber can have lengths of less than 12 millimeters; less than 10 millimeters, less than 6.5 millimeters, and less than 3.5 millimeters. The domains or segments in the, multicomponent fiber once separated yield the water non-dispersible polymer microfibers.
The instant invention also includes a fibrous article comprising the water- dispersible fiber, the multicomponent fiber, microdenier fibers, or water non- dispersible polymer microfibers described hereinabove. The term "fibrous article" is understood to mean any article having or resembling fibers. Non-limiting examples of fibrous articles include multifilament fibers, yarns, cords, tapes, fabrics, wet-laid webs, dry-laid webs, melt blown webs, spunbonded webs, thermobonded webs, hydroentangled webs, nonwoven webs and fabrics, and combinations thereof; items having one or more layers of fibers, such as, for example, multilayer nonwovens, laminates, and composites from such fibers, gauzes, bandages, diapers, training pants, tampons, surgical gowns and masks, feminine napkins; and the like. In addition, the water non-dispersible microdfibers can be utilized in filter media for air filtration, liquid filtration, filtration for food preparation, filtration for medical applications, and for paper making processes and paper products. Further, the fibrous articles may include replacement inserts for various personal hygiene and cleaning products. The fibrous article of the present invention may be bonded, laminated, attached to, or used in conjunction with other materials which may or may not be water-dispersible. The fibrous article, for example, a nonwoven fabric layer, may be bonded to a flexible plastic film or backing of a water non-dispersible material, such as polyethylene. Such an assembly, for example, could be used as one component of a disposable diaper. In addition, the fibrous article may result from overblowing fibers onto another substrate to form highly assorted combinations of engineered melt blown, spunbond, film, or membrane structures.
The fibrous articles of the instant invention include nonwoven fabrics and webs. A nonwoven fabric is defined as a fabric made directly from fibrous webs without weaving or knitting operations. The Textile Institue defines nonwovens as textile structures made directly from fibre rather than yarn. These fabrics are normally made from continuous filments or from fibre webs or batts strengthened by bonding using various techniques, which include, but are not limited to, adhesive bonding, mechanical interlocking by needling or fluid jet entanglement, thermal bonding, and stitch bonding. For example, the multicomponent fiber of the present invention may be formed into a fabric by any known fabric forming process. The resulting fabric or web may be converted into a microdenier fiber web by exerting sufficient force to cause the multicomponent fibers to split or by contacting the web with water to remove the sulfopolyester leaving the remaining microdenier fibers behind.
Our invention thus provides a process for a microdenier fiber web, comprising:
(A) spinning a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 570C and one or more water non-dispersible polymers immiscible with the sulfopolyester into multicomponent fibers, the sulfopolyester comprising:
(i) about 50 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid, based on the total acid residues;
(ii) about 4 to about 30 mole%, based on the total acid residues, of a residue of sodiosulfoisophthalic acid;
(iii) one or more diol residues wherein at least 25 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500; and
(iv) 0 to about 20 mole %, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof. wherein the multicomponent fibers have a plurality of segments comprising the water non-dispersible polymers wherein the segments are substantially isolated from each other by the sulfopolyester intervening between the segments; and the fiber contains less than 10 weight percent of a pigment or filler, based on the total weight of the fiber; (B) overlapping and collecting the multicomponent fibers of Step A to form a nonwoven web; and
(C) contacting the nonwoven web with water to remove the sulfopolyester thereby forming a microdenier fiber web.
In another embodiment of the invention, a process for a microdenier fiber web is provided which comprises:
(A) spinning at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with said sulfopolyester into multicomponent fibers, said multicomponent fibers have a plurality of domains comprising said water non-dispersible polymers wherein said domains are substantially isolated from each other by said sulfopolyester intervening between said domains; wherein said fiber has an as-spun denier of less than about 6 denier per filament; wherein said water dispersible sulfopolyester exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein said sulfopolyester comprising less than about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residues;
(B) collecting said multicomponent fibers of Step A) to form a non-woven web; and
(C) contacting said non-woven web with water to remove said sulfopolyester thereby forming a microdenier fiber web.
In another embodiment of the invention, a process for a microdenier fiber web is provided which comprises:
(A) extruding at least one water dispersible sulfopolyester and one or more water non-dispersible polymers immiscible with said water dispersible sulfopolyester into multicomponent extrudates, said multicomponent extrudates have a plurality of domains comprising said water non-dispersible polymers wherein said domains are substantially isolated from each other by said water dispersible sulfopolyester intervening between said domains;
(B) melt drawing said multicomponent extrudates at a speed of at least about 2000 m/min to produce multicomponent fibers; (C) collecting said multicomponent fibers of Step (B) to form a non-woven web; and
(D) contacting said non-woven web with water to remove said sulfopolyester thereby forming a microdenier fiber web.
The process also preferably comprises prior to Step (C) the step of hydroentangling the multicomponent fibers of the non- woven web. It is also preferable that the hydroentangling step results in a loss of less than about 20 wt. % of the sulfopolyester contained in the multicomponent fibers, more preferably this loss is less than 15 wt. %, and most preferably is less than 10 wt. %. In furtherance of the goal of reducing the loss of sulfopolyester during hydroentanglement, the water used during this process preferably has a temperature of less than about 45 °C, more preferably less than about 35°C, and most preferably less than about 30°C. It is preferable that the water used during hydroentanglement be as close to room temperature as possible to minimize loss of sulfopolyester from the multicomponent fibers. Conversely, removal of the sulfopolyester polymer during Step (C) is preferably carried out using water having a temperature of at least about 45°C, more preferably at least about 60°C, and most preferably at least about 80°C.
After hydroentanglement and prior to Step (C), the non-woven web may under go a heat setting step comprising heating the non- woven web to a temperature of at least about 100°C, and more preferably at least about 12O0C. The heat setting step relaxes out internal fiber stresses and aids in producing a dimensionally stable fabric product. It is preferred that when the heat set material is reheated to the temperature to which it was heated during the heat setting step that it exhibits surface area shrinkage of less than about 5% of its original surface area. More preferably, the shrinkage is less than about 2% of the original surface area, and most preferably the shrinkage is less than about 1%.
The sulfopolyester used in the multicomponent fiber can be any of those described herein, however, it is preferable that the sulfopolyester have a melt viscosity of less than about 6000 poise measured at 240°C at a strain rate of 1 rad/sec and comprise less than about 12 mole %, based on the total repeating units, of residues of at least one sulfomonomer. These types of sulfopolyesters are previously described herein.
Furthermore, the inventive method preferably comprises the step of drawing the multicomponent fiber at a fiber velocity of at least 2000 m/min, more preferably at least about 3000 m/min, even more preferably at least about 4000 m/min, and most preferably at least about 5000 m/min.
In another embodiment of this invention, nonwoven articles comprising water non-dispersible polymer microfibers can be produced. The nonwoven article comprises water non-dispersible polymer microfibers and is produced by a process selected from the group consisting of a dry-laid process and a wet-laid process. Multicomponent fibers and processes for producing water non-dispersible polymer microfibers were previously disclosed in the specification.
In one embodiment of the invention, at least 1% of the water non-dispersible polymer microfiber is contained in the nonwoven article. Other amounts of water non-dispersible polymer microfiber contained in the nonwoven article are at least 10%, at least 25%, and at least 50%.
In another aspect of the invention, the nonwoven article can further comprise at least one other fiber. The other fiber can be any that is known in the art depending on the type of nonwoven article to be produced. In one embodiment of the invention, the other fiber can be selected from the group consisting cellulosic fiber pulp, glass fiber, polyester fibers, nylon fibers, polyolefin fibers, rayon fibers cellulose ester fibers, and mixtures thereof.
The nonwoven article can also further comprise at least one additive. Additives include, but are not limited to, starches, fillers, and binders. Other additives are discussed in other sections of this disclosure.
Generally, manufacturing processes to produce these nonwoven articles from water non-dispersible microfibers produced from multicomponent fibers can be split into the following groups: dry-laid webs, wet-laid webs, and combinations of these processes with each other or other nonwoven processes.
Generally, dry-laid nonwoven articles are made with staple fiber processing machinery which is designed to manipulate fibers in the dry state. These include mechnical processes, such as, carding, aerodynamic, and other air-laid routes. Also included in this category are nonwoven articles made from filaments in the form of tow, and fabrics composed of staple fibers and stitching filaments or yards i.e. stitchbonded nonwovens. Carding is the process of disentangling, cleaning, and intermixing fibers to make a web for further processing into a nonwoven article. The process predominantly aligns the fibers which are held together as a web by mechanical entanglement and fiber-fiber friction. Cards are generally configured with one or more main cylinders, roller or stationary tops, one or more doffers, or various combinations of these principal components. On example of a card is a roller card. The carding action is the combing or working of the water non-dispersible polymer microfibers between the points of the card on a series of interworking card rollers. Other types of cards include woolen, cotton, and random cards. Garnetts can also be used to align these fibers.
The water non-dispersible polymer microfibers in the dried-laid process can also be aligned by air-laying. These fibers are directed by air current onto a collector which can be a flat conveyor or a drum.
Extrusion-formed webs can also be produced from the multicomponents fibers of this invention. Examples include spunbonded and melt-blown. Extrusion technology is used to produce spunbond, meltblown, and porous-film nonwoven articles. These nonwoven articles are made with machinery associated with polymer extrusion methods such as melt spinning, film casting, and extrusion coating. The nonwoven article is then contacted with water to remove the water dispersible sulfopolyester thus producing a nonwoven article comprising water non-dispersible polymer microfibers.
In the spunbond process, the water dispersible sulfopolyester and water non- dispersible polymer are transformed directly to fabric by extruding multicomponent filaments, orienting them as bundles or groupings, layering them on a conveying screen, and interlocking them. The interlocking can be conducted by thermal fusion, mechnical entanglement, hydroentangling, chemical binders, or combinations of these processes.
Meltblown fabrics are also made directly from the water dispersible sulfopolyester and the water non-dispersible polymer. The polymers are melted and extruded. As soon as the melt passes through the extrusion orifice, it is blown with air at high temperature. The air stream attenuates and solidifies the molten polymers. The multicomponent fibers can then be separated from the air stream as a web and compressed between heated rolls.
Combined spunbond and meltbond processes can also be utilized to produce nonwoven articles.
Wet laid processes involve the use of papermaking technology to produce nonwoven articles. These nonwoven articles are made with machinery associated with pulp fiberizing, such as hammer mills, and paperforming. For example, slurry pumping onto continous screens which are designed to manipulate short fibers in a fluid.
In one embodiment of the wet laid process,, water non-dispersible polymer microfibers are suspended in water, brought to a forming unit where the water is drained off through a forming screen, and the fibers are deposited on the screen wire.
In another embodiment of the wet laid process, water non-dispersible polymer microfibers are dewatered on a sieve or a wire mesh which revolves at the beginning of hydraulic formers over dewatering modules (suction boxes, foils and curatures) at high speeds of up to 1500 meters per minute. The sheet is then set on this wire and dewatering proceeds to a solid content of approximately 20-30%. The sheet can then be pressed and dried.
In another embodiment of the wet-laid process, a process is provided comprising: a) optionally, rinsing the water non-dispersible polymer microfibers with water ; b) adding water to the water non-dispersible polymer microfibers to produce a water non-dispersible polymer microfϊber slurry; c) optionally, adding other fibers and /or additives to water non-dispersible polymer microfibers or slurry; and d) transferring the water non-dispersible polymer microfibers containing slurry to a wet-laid nonwoven zone to produce the nonwoven article.
In Step a), the number of rinses depends on the particular use chosen for the water non-dispersible polymer microfibers. In Step b), sufficient water is added to the microfibers to allow them to be routed to the wet-laid nonwoven zone.
The wet-laid nonwoven zone comprises any equipment known in the art to produce wet-laid nonwoven articles. In one embodiment of the invention, the wet- laid nonwoven zone comprises at least one screen, mesh, or sieve in order to remove the water from the water non-dispersible polymer microfiber slurry.
In another embodiment of the invention, the water non-dispersible polymer microfiber slurry is mixed prior to transferring to the wet-laid nonwoven zone.
Web-bonding processes can also be utilized to produce nonwoven articles. These can be split into chemical and physical processes. Chemical bonding refers to the use of water-based and solvent-based polymers to bind together the fibers and/or fibrous webs. These binders can be applied by saturation, impregnation, spraying, printing, or application as a foam. Physical bonding processes include thermal processes such as calendaring and hot air bonding, and mechanical processes such as needling and hydroentangling. Needling or needle-punching processes mechanically interlock the fibers by physically moving some of the fibers from a near-horizontal to a near-vertical position. Needle-punching can be conducted by a needleloom. A needleloom generally contains a web-feeding mechanism, a needle beam which comprises a needleboard which holds the needles, a stripper plate, a bed plate, and a fabric take-up mechanism.
Stitchbonding is a mechanical bonding method that uses knitting elements, with or without yarn, to interlock the fiber webs. Examples of stitchbonding machines include, but are not limited to, Maliwatt, Arachne, Malivlies, and Arabeva.
The nonwoven article can be held together by 1) mechanical fiber cohesion and interlocking in a web or mat; 2) various techniques of fusing of fibers, including the use of binder fibers, utilizing the thermoplastic properties of certain polymers and polymer blends; 3) use of a binding resin such as starch, casein, a cellulose derivative, or a synthetic resin, such as an acrylic latex or urethane; 4) powder adhesive binders; or 5) combinations thereof. The fibers are often deposited in a random manner, although orientation in one direction is possible, followed by bonding using one of the methods described above.
The fibrous articles of our invention further also may comprise one or more layers of water-dispersible fibers, multicomponent fibers, or microdenier fibers. The fiber layers may be one or more nonwoven fabric layers, a layer of loosely bound overlapping fibers, or a combination thereof. In addition, the fibrous articles may include personal and health care products such as, but not limited to, child care products, such as infant diapers; child training pants; adult care products, such as adult diapers and adult incontinence pads; feminine care products, such as feminine napkins, panty liners, and tampons; wipes; fiber-containing cleaning products; medical and surgical care products, such as medical wipes, tissues, gauzes, examination bed coverings, surgical masks, gowns, bandages, and wound dressings; fabrics; elastomeric yarns, wipes, tapes, other protective barriers, and packaging material. The fibrous articles may be used to absorb liquids or may be pre-moistened with various liquid compositions and used to deliver these compositions to a surface. Non-limiting examples of liquid compositions include detergents; wetting agents; cleaning agents; skin care products, such as cosmetics, ointments, medications, emollients, and fragrances. The fibrous articles also may include various powders and particulates to improve absorbency or as delivery vehicles. Examples of powders and particulates include, but are not limited to, talc, starches, various water absorbent, water-dispersible, or water swellable polymers, such as super absorbent polymers, sulfopolyesters, and poly(vinylalcohols), silica, pigments, and microcapsules. Additives may also be present, but are not required, as needed for specific applications. Examples of additives include, but are not limited to, oxidative stabilizers, UV absorbers, colorants, pigments, opacifiers (delustrants), optical brighteners, fillers, nucleating agents, plasticizers, viscosity modifiers, surface modifiers, antimicrobials, disinfectants, cold flow inhibitors, branching agents, and catalysts.
In addition to being water-dispersible, the fibrous articles described above may be flushable. The term "flushable" as used herein means capable of being flushed in a conventional toilet, and being introduced into a municipal sewage or residential septic system, without causing an obstruction or blockage in the toilet or sewage system.
The fibrous article may further comprise a water-dispersible film comprising a second water-dispersible polymer. The second water-dispersible polymer may be the same as or different from the previously described water-dispersible polymers used in the fibers and fibrous articles of the present invention. In one embodiment, for example, the second water-dispersible polymer may be an additional sulfopolyester which, in turn, comprises:
(A) about 50 to about 96 mole% of one or more residues of isophthalic acid or terephthalic acid, based on the total acid residues;
(B) about 4 to about 30 mole%, based on the total acid residues, of a residue of sodiosulfoisophthalic acid;
(C) one or more diol residues wherein at least 15 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500;
(D) 0 to about 20 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof. The additional sulfopolyester may be blended with one or more supplemental polymers, as described hereinabove, to modify the properties of the resulting fibrous article. The supplemental polymer may or may not be water-dispersible depending on the application. The supplemental polymer may be miscible or immiscible with the additional sulfopolyester.
The additional sulfopolyester may contain other concentrations of isophthalic acid residues, for example, about 60 to about 95 mole%, and about 75 to about 95 mole%. Further examples of isophthalic acid residue concentrations ranges are about 70 to about 85 mole%, about 85 to about 95 mole% and about 90 to about 95 mole%. The additional sulfopolyester also may comprise about 25 to about 95 mole% of the residues of diethylene glycol. Further examples of diethylene glycol residue concentration ranges include about 50 to about 95 mole%, about 70 to about 95 mole%, and about 75 to about 95 mole%. The additional sulfopolyester also may include the residues of ethylene glycol and/or 1,4-cyclohexanedimethanol. Typical concentration ranges of CHDM residues are about 10 to about 75 mole%, about 25 to about 65 mole%, and about 40 to about 60 mole%. Typical concentration ranges of ethylene glycol residues are about 10 to about 75 mole%, about 25 to about 65 mole%, and about 40 to about 60 mole%. In another embodiment, the additional sulfopolyester comprises is about 75 to about 96 mole% of the residues of isophthalic acid and about 25 to about 95 mole% of the residues of diethylene glycol.
According to the invention, the sulfopolyester film component of the fibrous article may be produced as a monolayer or multilayer film. The monolayer film may be produced by conventional casting techniques. The multilayered films may be produced by conventional lamination methods or the like. The film may be of any convenient thickness, but total thickness will normally be between about 2 and about 50 mil.
The film-containing fibrous articles may include one or more layers of water- dispersible fibers as described above. The fiber layers may be one or more nonwoven fabric layers, a layer of loosely bound overlapping fibers, or a combination thereof. In addition, the film-containing fibrous articles may include personal and health care products as described hereinabove.
As described previously, the fibrous articles also may include various powders and particulates to improve absorbency or as delivery vehicles. Thus, in one embodiment, our fibrous article comprises a powder comprising a third water- dispersible polymer that may be the same as or different from the water-dispersible polymer components described previously herein. Other examples of powders and particulates include, but are not limited to, talc, starches, various water absorbent, water-dispersible, or water swellable polymers, such as poly(acrylonitiles), sulfopolyesters, and poly(vinyl alcohols), silica, pigments, and microcapsules.
Our novel fiber and fibrous articles have many possible uses in addition to the applications described above. One novel application involves the melt blowing a film or nonwoven fabric onto flat, curved, or shaped surfaces to provide a protective layer. One such layer might provide surface protection to durable equipment during shipping. At the destination, before putting the equipment into service, the outer layers of sulfopolyester could be washed off. A further embodiment of this general application concept could involve articles of personal protection to provide temporary barrier layers for some reusable or limited use garments or coverings. For the military, activated carbon and chemical absorbers could be sprayed onto the attenuating filament pattern just prior to the collector to allow the melt blown matrix to anchor these entities on the exposed surface. The chemical absorbers can even be changed in the forward operations area as the threat evolves by melt blowing on another layer.
A major advantage inherent to sulfopolyesters is the facile ability to remove or recover the polymer from aqueous dispersions via flocculation or precipitation by adding ionic moieties (i.e., salts). Other methods, such as pH adjustment, adding nonsolvents, freezing, and so forth may also be employed. Therefore, fibrous articles, such as outer wear protective garments, after successful protective barrier use and even if the polymer is rendered as hazardous waste, can potentially be handled safely at much lower volumes for disposal using accepted protocols, such as incineration.
Undissolved or dried sulfopolyesters are known to form strong adhesive bonds to a wide array of substrates, including, but not limited to fluff pulp, cotton, acrylics, rayon, lyocell, PLA (polylactides), cellulose acetate, cellulose acetate propionate, poly(ethylene) terephthalate, poly(butylene) terephthalate, poly(trimethylene) terephthalate, poly(cyclohexylene) terephthalate, copolyesters, polyamides (nylons), stainless steel, aluminum, treated polyolefins, PAN (polyacrylonitriles), and polycarbonates. Thus, our nonwoven fabrics may be used as laminating adhesives or binders that may be bonded by known techniques, such as thermal, radio frequency (RF), microwave, and ultrasonic methods. Adaptation of sulfopoly esters to enable RF activation is disclosed in a number of recent patents. Thus, our novel nonwoven fabrics may have dual or even multifunctionality in addition to adhesive properties. For example, a disposable baby diaper could be obtained where a nonwoven of the present invention serves as both an water-responsive adhesive as well as a fluid managing component of the final assembly.
Our invention also provides a process for water-dispersible fibers comprising: (A) heating a water-dispersible polymer composition to a temperature above its flow point, wherein the polymer composition comprises:
(i) residues of one or more dicarboxylic acids;
(ii) about 4 to about 40 mole%, based on the total repeating units, of residues of at least one sulfomonomer having 2 functional groups and one or more metal sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof; and
(iii) one or more diol residues wherein at least 20 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range/of 2 to about 500; (iv) 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof; wherein the polymer composition contains less than 10 weight percent of a pigment or filler, based on the total weight of the polymer composition; and (II) melt spinning filaments. As described hereinabove, a water-dispersible polymer, optionally, may be blended with the sulfopolyester. In addition, a water non-dispersible polymer, optionally, may be blended with the sulfopolyester to form a blend such that blend is an immiscible blend. The term "flow point", as used herein, means the temperature at which the viscosity of the polymer composition permits extrusion or other forms of processing through a spinneret or extrusion die. The dicarboxylic acid residue may comprise from about 60 to about 100 mole% of the acid residues depending on the type and concentration of the sulfomonomer. Other examples of concentration ranges of dicarboxylic acid residues are from about 60 mole% to about 95 mole% and about 70 mole% to about 95 mole%. The preferred dicarboxylic acid residues are isophthalic, terephthalic, and 1 ,4-cyclohexane- dicarboxylic acids or if diesters are used, dimethyl terephthalate, dimethyl isophthalate, and dimethyl- 1 ,4-cyclohexanedicarboxylate with the residues of isophthalic and terephthalic acid being especially preferred.
The sulfomonomer may be a dicarboxylic acid or ester thereof containing a sulfonate group, a diol containing a sulfonate group, or a hydroxy acid containing a sulfonate group. Additional examples of concentration ranges for the sulfomonomer residues are about 4 to about 25 mole%, about 4 to about 20 mole%, about 4 to about 15 mole%, and about 4 to about 10 mole%, based on the total repeating units. The cation of the sulfonate salt may be a metal ion such as Li+, Na+, K+, Mg+"1", Ca+^ Ni"1"1", Fe+*, and the like. Alternatively, the cation of the sulfonate salt may be non-metallic such as a nitrogenous base as described previously. Examples of sulfomonomer residues which may be used in the process of the present invention are the metal sulfonate salt of sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalic acid, or combinations thereof. Another example of sulfomonomer which may be used is 5- sodiosulfoisophthalic acid or esters thereof. If the sulfomonomer residue is from 5- sodiosulfoisophthalic acid, typical sulfomonomer concentration ranges are about 4 to about 35 mole%, about 8 to about 30 mole %, and about 10 to 25 mole %, based on the total acid residues.
The sulfopolyester of our includes one or more diol residues which may include aliphatic, cycloaliphatic, and aralkyl glycols. The cycloaliphatic diols, for example, 1,3- and 1,4-cyclohexanedimethanol, may be present as their pure cis or trans isomers or as a mixture of cis and trans isomers. Non-limiting examples of lower molecular weight polyethylene glycols, e.g., wherein n is from 2 to 6, are diethylene glycol, triethylene glycol, and tetraethylene glycol. Of these lower molecular weight glycols, diethylene and triethylene glycol are most preferred. The sulfopolyester may optionally include a branching monomer. Examples of branching monomers are as described hereinabove. Further examples of branching monomer concentration ranges are from 0 to about 20 mole% and from 0 to about 10 mole%. The sulfopolyester of our novel process has a Tg of at least 250C. Further examples of glass transition temperatures exhibited by the sulfopolyester are at least 3O0C, at least 350C, at least 4O0C, at least 5O0C, at least 6O0C, at least 650C, at least 8O0C, and at least 9O0C. Although other Tg's are possible, typical glass transition temperatures of the dry sulfopolyesters our invention are about 300C, about 480C, about 550C, about 650C, about 7O0C, about 750C, about 850C, and about 9O0C.
The water-dispersible fibers are prepared by a melt blowing process. The polymer is melted in an extruder and forced through a die. The extrudate exiting the die is rapidly attenuated to ultrafine diameters by hot, high velocity air. The orientation, rate of cooling, glass transition temperature (Tg), and rate of crystallization of the fiber are important because they affect the viscosity and processing properties of the polymer during attenuation. The filament is collected on a renewable surface, such as a moving belt, cylindrical drum, rotating mandrel, and so forth. Predrying of pellets (if needed), extruder zone temperature, melt temperature, screw design, throughput rate, air temperature, air flow (velocity), die air gap and set back, nose tip hole size, die temperature, die-to-collector (DCP) distance, quenching environment, collector speed, and post treatments are all factors that influence product characteristics such as filament diameters, basis weight, web thickness, pore size, softness, and shrinkage. The high velocity air also may be used to move the filaments in a somewhat random fashion that results in extensive interlacing. If a moving belt is passed under the die, a nonwoven fabric can be produced by a combination of overlapping laydown, mechanical cohesiveness, and thermal bonding of the filaments. Overblowing onto another substrate, such as a spunbond or backing layer, is also possible. If the filaments are taken up on an rotating mandrel, a cylindrical product is formed. A water-dispersible fiber lay-down can also be prepared by the spunbond process.
The instant invention, therefore, further provides a process for water-dispersible, nonwoven fabric comprising: (A) heating a water-dispersible polymer composition to a temperature above its flow point, wherein the polymer composition comprises:
(i) residues of one or more dicarboxylic acids;
(ii) about 4 to about 40 mole%, based on the total repeating units, of residues of at least one sulfomonomer having 2 functional groups and one or more metal sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
(iii) one or more diol residues wherein at least 20 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)π-OH wherein n is an integer in the range of 2 to about 500;
(iv) 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof; wherein the sulfopolyester has a glass transition temperature (Tg) of at least 250C; wherein the polymer composition contains less than 10 weight percent of a pigment or filler, based on the total weight of the polymer composition;
(B) melt-spinning filaments; and
(C) overlapping and collecting the filaments of Step (B) to form a nonwoven fabric. As described hereinabove, a water-dispersible polymer, optionally, may be blended with the sulfopolyester. In addition, a water non-dispersible polymer, optionally, may be blended with the sulfopolyester to form a blend such that blend is an immiscible blend. The dicarboxylic acid, sulfomonomer, and branching monomer residues are as described previously. The sulfopolyester has a Tg of at least 250C. Further examples of glass transition temperatures exhibited by the sulfopolyester are at least 3O0C, at least 350C, at least 4O0C, at least 5O0C, at least 6O0C, at least 650C, at least 8O0C, and at least 9O0C. Although other Tg's are possible, typical glass transition temperatures of the dry sulfopolyesters our invention are about 3O0C, about 480C, about 550C, about 650C, about 7O0C, about 750C, about 850C, and about 9O0C. The invention is further illustrated by the following examples. EXAMPLES
All pellet samples were predried under vacuum at room temperature for at least 12 hours. The dispersion times shown in Table 3 are for either complete dispersion or dissolution of the non woven fabric samples. The abbreviation "CE", used in Tables 2 and 3 mean "comparative example". Example 1
A sulfopolyester containing 76 mole%, isophthalic acid, 24 mole% of sodio- sulfoisophthalic acid, 76 mole% diethylene glycol, and 24 mole% 1 ,4-cyclohexane- dimethanol with an Ih. V. of 0.29 and a Tg of 480C was meltblown through a nominal 6-inch die (30 holes/inch in the nosepiece) onto a cylindrical collector using the conditions shown in Table 1. Interleafing paper was not required. A soft, handleable, flexible web was obtained that did not block during the roll winding operation. Physical properties are provided in Table 2. A small piece (I" x 3") of the nonwoven fabric was easily dispersed in both room temperature (RT) and 5O0C water with slight agitation as shown by data in Table 3.
Table 1 - Melt Blowin Conditions
Figure imgf000074_0001
Figure imgf000075_0001
Table 2 - Physical Properties of Nonwovens
Figure imgf000075_0002
Table 3 - Dispensability of Nonwovens
Figure imgf000075_0003
Figure imgf000076_0001
Example 2
A sulfopolyester containing 89 mole%, isophthalic acid, 1 1 mole% of sodiosulfoisophthalic acid, 72 mole% diethylene glycol, and 28 mole% ethylene glycol with an Ih.V. of 0.4 and a Tg of 350C was meltblown through a 6-inch die using conditions similar to those in Table 1. A soft, handleable, flexible web was obtained that did not block during a roll winding operation. Physical properties are provided in Table 2. A small piece (I" x 2") of the nonwoven fabric was easily and completely dispersed at 500C and 800C; at RT (230C), the fabric required a longer period of time for complete dispersion as shown by the data in Table 3.
It was found that the compositions in Examples 1 and 2 can be overblown onto other nonwoven substrates. It is also possible to condense and wrap shaped or contoured forms that are used instead of conventional web collectors. Thus, it is possible to obtain circular "roving" or plug forms of the webs.
Comparative Examples 1-3
Pellets of a sulfopolyester containing 89 mole%, isophthalic acid, 1 1 mole% of sodiosulfoisophthalic acid, 72 mole% diethylene glycol, and 28 mole% ethylene glycol with an Ih.V. of 0.4 and a Tg of 350C were combined with polypropylene (Basell PF 008) pellets in bicomponent ratios (by wt%) of :
75 PP : 25 sulfopolyester (Example 3)
50 PP : 50 sulfopolyester (Example 4) 25 PP : 75 sulfopolyester (Example 5)
The PP had a MFR (melt flow rate) of 800. A melt blowing operation was performed on a line equipped with a 24-inch wide die to yield handleable, soft, flexible, but nonblocking webs with the physical properties provided in Table 2. Small pieces (I" x 4") of nonwoven fabric readily disintegrated as reported in Table 3. None of the fibers, however, were completely water-dispersible because of the insoluble polypropylene component.
Example 3
A circular piece (4" diameter) of the nonwoven produced in Example 2 was used as an adhesive layer between two sheets of cotton fabric. A Hannifin melt press was used to fuse the two sheets of cotton together by applying a pressure 35 psig at 2000C for 30 seconds. The resultant assembly exhibited exceptionally strong bond strength. The cotton substrate shredded before adhesive or bond failure. Similar results have also been obtained with other cellulosics and with PET polyester substrates. Strong bonds were also produced by ultrasonic bonding techniques.
Comparative Example 4
A PP (Exxon 3356G) with a 1200 MFR was melt blown using a 24" die to yield a flexible nonwoven fabric that did not block and was easily unwound from a roll. Small pieces (I" x 4") did not show any response (i.e., no disintegration or loss in basis weight) to water when immersed in water at RT or 500C for 15 minutes.
Example 4 >
Unicomponent fibers of a sulfopolyester containing 82 mole% isophthalic acid, 18 mole% of sodiosulfoisophthalic acid, 54 mole% diethylene glycol, and 46 mole% 1 ,4-cyclohexanedimethanol with a Tg of 550C were melt spun at melt temperatures of 2450C (473 F) on a lab staple spinning line. As-spun denier was approximately 8 d/f. Some blocking was encountered on the take-up tubes, but the 10-filament strand readily dissolved within 10 - 19 seconds in unagitated, demineralized water at 820C and a pH between 5 and 6.
Example 5
Unicomponent fibers obtained from a blend (75:25) of a sulfopolyester containing 82 mole% isophthalic acid, 18 mole% of sodiosulfoisophthalic acid, 54 mole% diethylene glycol, and 46 mole% 1 ,4-cyclohexanedimethanol (Tg of 550C) and a sulfopolyester containing 91 mole% isophthalic acid, 9 mole% of sodiosulfoisophthalic acid, 25 mole% diethylene glycol, and 75 mole% 1,4- cyclohexanedimethanol (Tg of 650C), respectively, were melt spun on a lab staple spinning line. The blend has a Tg of 570C as calculated by taking a weighted average of the Tg's of the component sulfopolyesters. The 10-filament strands did not show any blocking on the take-up tubes, but readily dissolved within 20 — 43 seconds in unagitated, demineralized water at 82° C and a pH between 5 and 6.
Example 6
The blend described in Example 5 was co-spun with PET to yield bicomponent islands-in-the-sea fibers. A configuration was obtained where the sulfopolyester "sea" is 20 wt% of the fiber containing 80 wt% of PET "islands". The spun yarn elongation was 190% immediately after spinning. Blocking was not encountered as the yarn was satisfactorily unwound from the bobbins and processed a week after spinning. In a subsequent operation, the "sea" was dissolved by passing the yarn through an 880C soft water bath leaving only fine PET filaments.
Example 7
This prophetic example illustrates the possible application of the multicomponent and microdenier fibers of the present invention to the preparation of specialty papers. The blend described in Example 5 is co-spun with PET to yield bicomponent islands-in-the-sea fibers. The fiber contains approximately 35 wt% sulfopolyester "sea" component and approximately 65 wt% of PET "islands". The uncrimped fiber is cut to 1/8 inch lengths. In simulated papermaking, these short-cut bicomponent fibers are added to the refining operation. The sulfopolyester "sea" is removed in the agitated, aqueous slurry thereby releasing the microdenier PET fibers into the mix. At comparable weights, the microdenier PET fibers ("islands") are more effective to increase paper tensile strength than the addition of coarse PET fibers.
Comparative Example 8
Bicomponent fibers were made having a 108 islands in the sea structure on a spunbond line using a 24" wide bicomponent spinneret die from Hills Inc., Melbourne, FL, having a total of 2222 die holes in the die plate. Two extruders were connected to melt pumps which were in turn connected to the inlets for both components in the fiber spin die. The primary extruder (A) was connected to the inlet which metered a flow of Eastman F61HC PET polyester to form the island domains in the islands in the sea fiber cross-section structure. The extrusion zones were set to melt the PET entering the die at a temperature of 285°C. The secondary extruder (B) processed Eastman AQ 55 S sulfopolyester polymer from Eastman Chemical Company, Kingsport, TN having an inherent viscosity of about 0.35 and a melt viscosity of about 15,000 poise, measured at 240°C and 1 rad/sec sheer rate and 9,700 poise measured at 240°C and 100 rad/sec sheer rate in a Rheometric Dynamic Analyzer RDAII (Rheometrics Inc. Piscataway, New Jersey) rheometer. Prior to performing a melt viscosity measurement, the sample was dried for two days in a vacuum oven at 600C. The viscosity test was performed using a 25 mm diameter parallel-plate geometry at lmm gap setting. A dynamic frequency sweep was run at a strain rate range of 1 to 400 rad/sec and 10% strain amplitude. Then, the viscosity was measured at 240° C and strain rate of 1 rad/sec. This procedure was followed in determining the viscosity of the sulfopolyester materials used in the subsequent examples. The secondary extruder was set to melt and feed the AQ 55S polymer at a melt temperature of 255°C to the spinnerette die. The two polymers were formed into bicomponent extrudates by extrusion at a throughput rate of 0.6 g/hole/min. The volume ratio of PET to AQ 55S in the bicomponent extrudates was adjusted to yield 60/40 and 70/30 ratios. An aspirator device was used to melt draw the bicomponent extrudates to produce the bicomponent fibers. The flow of air through the aspirator chamber pulled the resultant fibers down. The amount of air flowing downward through the aspirator assembly was controlled by the pressure of the air entering the aspirator. In this example, the maximum pressure of the air used in the aspirator to melt draw the bicomponent extrudates was 25 psi. Above this value, the airflow through the aspirator caused the extrudates to break during this melt draw spinning process as the melt draw rate imposed on the bicomponent extrudates was greater than the inherent ductility of the bicomponent extrudates. The bicomponent fibers were laid down into a non-woven web having a fabric weight of 95 grams per square meter (gsm). Evaluation of the bicomponent fibers in this nonwoven web by optical microscopy showed that the PET was present as islands in the center of the fiber structure, but the PET islands around the outer periphery of the bicomponent fiber nearly coalesced together to form a nearly continuous ring of PET polymer around the circumference of the fibers which is not desireable. Microscopy found that the diameter of the bicomponent fibers in the nonwoven web was generally between 15-19 microns, corresponding to an average fiber as-spun denier of about 2.5 denier per filament (dpf). This represents a melt drawn fiber speed of about 2160 meters per minute. As- spun denier is defined as the denier of the fiber (weight in grams of 9000 meters length of fiber) obtained by the melt extrusion and melt drawing steps. The variation in bicomponent fiber diameter indicated non-uniformity in spun-drawing of the fibers.
The non-woven web samples were conditioned in a forced-air oven for five minutes at 120°C. The heat treated web exhibited significant shrinkage with the area of the nonwoven web being decreased to only about 12% of the initial area of the web before heating. Although not intending to be bound by theory, due to the high molecular weight and melt viscosity of the AQ 55S sulfopolyester used in the fiber, the bicomponent extrudates could not be melt drawn to the degree required to cause strain induced crystallization of the PET segments in the fibers. Overall, the AQ 55S sulfopolyester having this specific inherent viscosity and melt viscosity was not acceptable as the bicomponent extrudates could not be uniformly melt drawn to the desired fine denier.
Example 8
A sulfopolyester polymer with the same chemical composition as commercial Eastman AQ55S polymer was produced, however, the molecular weight was controlled to a lower value characterized by an inherent viscosity of about 0.25. The melt viscosity of this polymer was 3300 poise measured at 240°C and 1 rad/sec shear rate.
Example 9
Bicomponent extrudates having a 16-segment segmented pie structure were made using a bicomponent spinneret die from Hills Inc., Melbourne, FL, having a total of 2222 die holes in the 24 inch wide die plate on a spunbond equipment. Two extruders were used to melt and feed two polymers to this spinnerette die. The primary extruder (A) was connected to the inlet which fed Eastman F61HC PET polyester melt to form the domains or segment slices in the segmented pie cross- section structure. The extrusion zones were set to melt the PET entering the spinnerette die at a temperature of 285°C. The secondary extruder (B) melted and fed the sulfopolyester polymer of Example 8. The secondary extruder was set to extrude the sulfopolyester polymer at a melt temperature of 255°C into the spinnerette die. Except for the spinnerette die used and melt viscosity of the sulfopolyester polymer, the procedure employed in this example was the same as in Comparative Example 8. The melt throughput per hole was 0.6 gm/min. The volume ratio of PET to sulfopolyester in the bicomponent extrudates was set at 70/30 which represents a weight ratio of about 70/30.
The bicomponent extrudates were melt drawn using the same aspirator used in Comparative Example 8 to produce the bicomponent fibers. Initially, the input air to the aspirator was set to 25 psi and the fibers had as-spun denier of about 2.0 with the bicomponent fibers exhibiting a uniform diameter profile of about 14-15 microns. The air to the aspirator was increased to a maximum available pressure of 45 psi without breaking the melt extrudates during melt drawing. Using 45 psi air, the bicomponent extrudates were melt drawn down to a fiber as-spun denier of about 1.2 with the bicomponent fibers exhibiting a diameter of 1 1-12 microns when viewed under a microscope. The speed during the melt draw process was calculated to be about 4500 m/min. Although not intending to be bound by theory, at melt draw rates approaching this speed, it is believed that strain induced crystallization of the PET during the melt drawing process begins to occur. As noted above, it is desirable to form some oriented crystallinity in the PET fiber segments during the fiber melt draw process so that the nonwoven web will be more dimensionally stable during subsequent processing.
The bicomponent fibers using 45 psi aspirator air pressure were laid down into a nonwoven web with a weight of 140 grams per square meter (gsm). The shrinkage of the nonwoven web was measured by conditioning the material in a forced-air oven for five minutes at 120°C. This example represents a significant reduction in shrinkage compared to the fibers and fabric of Comparative Example 8.
This nonwoven web having 140 gsm fabric weight was soaked for five minutes in a static deionized water bath at various temperatures. The soaked nonwoven web was dried, and the percent weight loss due to soaking in deionized water at the various temperatures was measured as shown in Table 4.
Table 4
Figure imgf000083_0001
The sulfopolyester dissipated very readily into deionized water at a temperature of about 25°C. Removal of the sulfopolyester from the bicomponent fibers in the nonwoven web is indicated by the % weight loss. Extensive or complete removal of the sulfopolyester from the bicomponent fibers were observed at temperatures at or above 33°C. If hydroentanglement is used to produce a nonwoven web of these bicomponent fibers comprising the present sulfopolyester polymer of Example 8, it would be expected that the sulfopolyester polymer would be extensively or completely removed by the hydroentangling water jets if the water temperature was above ambient. If it is desired that very little sulfopolyester polymer be removed from these bicomponent fibers during the hydroentanglement step, low water temperature, less than about 25°C , should be used. Example 10
A sulfopolyester polymer was prepared with the following diacid and diol composition: diacid composition (71 mol % terephthalic acid, 20 mol % isophthalic acid, and 9 mol % 5-(sodiosulfo) isophthalic acid) and diol composition (60 mol % ethylene glycol and 40 mol % diethylene glycol). The sulfopolyester was prepared by high temperature polyesterification under vacuum. The esterification conditions were controlled to produce a sulfopolyester having an inherent viscosity of about 0.31. The melt viscosity of this sulfopolyester was measured to be in the range of about 3000- 4000 poise at 240°C and 1 rad/sec shear rate.
Example 11
The sulfopolyester polymer of Example 10 was spun into bicomponent segmented pie fibers and nonwoven web according to the same procedure described in Example 9. The primary extruder (A) fed Eastman F61HC PET polyester melt to form the larger segment slices in the segmented pie structure. The extrusion zones were set to melt the PET entering the spinnerette die at a temperature of 285°C. The secondary extruder (B) processed the sulfopolyester polymer of Example 10 which was fed at a melt temperature of 255°C into the spinnerette die. The melt throughput rate per hole was 0.6 gm/min. The volume ratio of PET to sulfopolyester in the bicomponent extrudates was set at 70/30 which represents the weight ratio of about 70/30. The cross-section of the bicomponent extrudates had wedge shaped domains of PET with sulfopolyester polymer separating these domains.
The bicomponent extrudates were melt drawn using the same aspirator assembly used in Comparative Example 8 to produce the bicomponent fiber. The maximum available pressure of the air to the aspirator without breaking the bicomponent fibers during drawing was 45 psi. Using 45 psi air, the bicomponent extrudates were melt drawn down to bicomponent fibers with as-spun denier of about 1.2 with the bicomponent fibers exhibiting a diameter of about 11-12 microns when viewed under a microscope. The speed during the melt drawing process was calculated to be about 4500 m/min. The bicomponent fibers were laid down into nonwoven webs having weights of 140 gsm and 110 gsm. The shrinkage of the webs was measured by conditioning the material in a forced-air oven for five minutes at 120°C. The area of the nonwoven webs after shrinkage was about 29% of the webs' starting areas.
Microscopic examination of the cross section of the melt drawn fibers and fibers taken from the nonwoven web displayed a very good segmented pie structure where the individual segments were clearly defined and exhibited similar size and shape. The PET segments were completely separated from each other so that they would form eight separate PET monocomponent fibers having a pie-slice shape after removal of the sulfopolyester from the bicomponent fiber.
The nonwoven web, having 110 gsm fabric weight, was soaked for eight minutes in a static deionized water bath at various temperatures. The soaked nonwoven web was dried and the percent weight loss due to soaking in deionized water at the various temperatures was measured as shown in Table 5.
Table 5
Figure imgf000085_0001
The sulfopolyester polymer dissipated very readily into deionized water at temperatures above about 46°C, with the removal of the sulfopolyester polymer from the fibers being very extensive or complete at temperatures above 51 °C as shown by the weight loss. A weight loss of about 30% represented complete removal of the sulfopolyester from the bicomponent fibers in the nonwoven web. If hydroentanglement is used to process this non- woven web of bicomponent fibers comprising this sulfopolyester, it would be expected that the polymer would not be extensively removed by the hydroentangling water jets at water temperatures below 40°C.
Example 12 The nonwoven webs of Example 1 1 having basis weights of both 140 gsm and 110 gsm were hydroentangled using a hydroentangling apparatus manufactured by Fleissner, GmbH, Egelsbach, Germany. The machine had five total hydroentangling stations wherein three sets of jets contacted the top side of the nonwoven web and two sets of jets contacted the opposite side of the nonwoven web. The water jets comprised a series of fine orifices about 100 microns in diameter machined in two- feet wide jet strips. The water pressure to the jets was set at 60 bar (Jet Strip # 1), 190 bar (Jet Strips # 2 and 3), and 230 bar (Jet Strips # 4 and 5). During the hydroentanglement process, the temperature of the water to the jets was found to be in the range of about 40-45°C. The nonwoven fabric exiting the hydroentangling unit was strongly tied together. The continuous fibers were knotted together to produce a hydroentangled nonwoven fabric with high resistance to tearing when stretched in both directions.
Next, the hydroentangled nonwoven fabric was fastened onto a tenter frame comprising a rigid rectangular frame with a series of pins around the periphery thereof. The fabric was fastened to the pins to restrain the fabric from shrinking as it was heated. The frame with the fabric sample was placed in a forced-air oven for three minutes at 130°C to cause the fabric to heat set while being restrained. After heat setting, the conditioned fabric was cut into a sample specimen of measured size, and the specimen was conditioned at 130°C without restraint by a tenter frame. The dimensions of the hydroentangled nonwoven fabric after this conditioning were measured and only minimal shrinkage (<0.5% reduction in dimension) was observed. It was apparent that heat setting of the hydroentangled nonwoven fabric was sufficient to produce a dimensionally stable nonwoven fabric.
The hydroentangled nonwoven fabric, after being heat set as described above, was washed in 90°C deionized water to remove the sulfopolyester polymer and leave the PET monocomponent fiber segments remaining in the hydroentangled fabric. After repeated washings, the dried fabric exhibited a weight loss of approximately 26 %. Washing the nonwoven web before hydroentangling demonstrated a weight loss of 31.3 %. Therefore, the hydroentangling process removed some of the sulfopolyester from the nonwoven web, but this amount was relatively small. In order to lessen the amount of sulfopolyester removed during hydroentanglement, the water temperature of the hydroentanglement jets should be lowered to below 40°C.
The sulfopolyester of Example 10 was found to give segmented pie fibers having good segment distribution where the water non-dispersable polymer segments formed individual fibers of similar size and shape after removal of the sulfopolyester polymer. The rheology of the sulfopolyester was suitable to allow the bicomponent extrudates to be melt drawn at high rates to achieve fine denier bicomponent fibers with as-spun denier as low as about 1.0. These bicomponent fibers are capable of being laid down into a non-woven web which could be hydroentangled without experiencing significant loss of sulfopolyester polymer to produce the nonwoven fabric. The nonwoven fabric produced by hydroentangling the non- woven web exhibited high strength and could be heat set at temperatures of about 120°C or higher to produce nonwoven fabric with excellent dimensional stability. The sulfopolyester polymer was removed from the hydroentangled nonwoven fabric in a washing step. This resulted in a strong nonwoven fabric product with lighter fabric weight and much greater flexibility and softer hand. The monocomponent PET fibers in this nonwoven fabric product were wedge shaped and exhibited an average denier of about 0.1.
Example 13
A sulfopolyester polymer was prepared with the following diacid and diol composition: diacid composition (69 mol % terephthalic acid, 22.5 mol % isophthalic acid, and 8.5 mol % 5-(sodiosulfo) isophthalic acid) and diol composition (65 mol % ethylene glycol and 35 mol % diethylene glycol). The sulfopolyester was prepared by high temperature polyesterifϊcation under vacuum. The esterification conditions were controlled to produce a sulfopolyester having an inherent viscosity of about 0.33. The melt viscosity of this sulfopolyester was measured to be in the range of about 3000- 4000 poise at 240°C and 1 rad/sec shear rate.
Example 14 The sulfopolyester polymer of Example 13 was spun into bicomponent islands-in-sea cross-section configuration with 16 islands on a spunbond line. The primary extruder (A) fed Eastman F61HC PET polyester melt to form the islands in the islands-in-sea structure. The extrusion zones were set to melt the PET entering the spinnerette die at a temperature of about 29O0C. The secondary extruder (B) processed the sulfopolyester polymer of Example 13 which was fed at a melt temperature of about 260°C into the spinnerette die. The volume ratio of PET to sulfopolyester in the bicomponent extrudates was set at 70/30 which represents the weight ratio of about 70/30. The melt throughput rate through the spinneret was 0.6 g/hole/minute. The cross-section of the bicomponent extrudates had round shaped island domains of PET with sulfopolyester polymer separating these domains.
The bicomponent extrudates were melt drawn using an aspirator assembly. The maximum available pressure of the air to the aspirator without breaking the bicomponent fibers during melt drawing was 50 psi. Using 50 psi air, the bicomponent extrudates were melt drawn down to bicomponent fibers with as-spun denier of about 1.4 with the bicomponent fibers exhibiting a diameter of about 12 microns when viewed under a microscope. The speed during the drawing process was calculated to be about 3900 m/min.
Example 15
The sulfopolyester polymer of Example 13 was spun into bicomponent islands- in-the- sea cross-section fibers with 64 islands fibers using a bicomponent extrusion line. The primary extruder fed Eastman F61HC polyester melt to form the islands in the islands-in-the-sea fiber cross- section structure. The secondary extruder fed the sulfopolyester polymer melt to form the sea in the islands-in-sea bicomponent fiber. The inherent viscosity of polyester was 0.61 dL/g while the melt viscosity of dry sulfopolyester was about 7000 poise measured at 240°C and 1 rad/sec strain rate using the melt viscosity measurement procedure described earlier. These islands-in-sea bicomponent fibers were made using a spinneret with 198 holes and a throughput rate of 0.85 gms/minute/hole. The polymer ratio between "islands" polyester and "sea" sulfopolyester was 65% to 35%. These bicomponent fibers were spun using an extrusion temperature of 280°C for the polyester component and 260°C for the sulfopolyester component. The bicomponent fiber contains a multiplicity of filaments (198 filaments) and was melt spun at a speed of about 530 meters/minute, forming filaments with a nominal denier per filament of about 14. A finish solution of 24 wt% PT 769 finish from Goulston Technologies was applied to the bicomponent fiber using a kiss roll applicator. The filaments of the bicomponent fiber were then drawn in line using a set of two godet rolls, heated to 90°C and 1300C respectively, and the final draw roll operating at a speed of about 1750 meters/minute, to provide a filament draw ratio of about 3.3X forming the drawn islands-in-sea bicomponent filaments with a nominal denier per filament of about 4.5 or an average diameter of about 25 microns. These filaments comprised the polyester microfiber "islands" having an average diameter of about 2.5 microns.
Example 16
The drawn islands-in-sea bicomponent fibers of Example 15 were cut into short length fibers of 3.2 millimeters and 6.4 millimeters cut lengths, thereby, producing short length bicomponent fibers with 64 islands-in-sea cross-section configurations. These short cut bicomponent fibers comprised "islands" of polyester and "sea" of water dispersible sulfopolyester polymer. The cross-sectional distribution of islands and sea was essentially consistent along the length of these short cut bicomponent fibers.
Example 17
The drawn islands-in-sea bicomponent fibers of Example 15 were soaked in soft water for about 24 hours and then cut into short length fibers of 3.2 millimeters and 6.4 millimeters cut lengths. The water dispersible sulfopolyester was at least partially emulsified prior to cutting into short length fibers. Partial separation of islands from the sea component was therefore effected, thereby, producing partially emulsified short length islands-in-sea bicomponent fibers.
Example 18
The short cut length islands-in-sea bicomponent fibers of Example 16 were washed using soft water at 800C to remove the water dispersible sulfopolyester "sea" component, thereby, releasing the polyester microfibers which were the "islands" component of the bicomponent fibers. The washed polyester microfibers were rinsed using soft water at 25°C to essentially remove most of the "sea" component. The optical microscopic observation of the washed polyester microfibers showed an average diameter of about 2.5 microns and lengths of 3.2 and 6.4 millimeters.
Example 19
The short cut length partially emulsified islands-in-sea bicomponent fibers of Example 17 were washed using soft water at 80°C to remove the water dispersible sulfopolyester "sea" component, thereby, releasing the polyester microfibers which were the "islands" component of the fibers. The washed polyester microfibers were rinsed using soft water at 25°C to essentially remove most of the "sea" component. The optical microscopic observation of the washed polyester microfibers showed polyester microfibers of average diameter of about 2.5 microns and lengths of 3.2 and 6.4 millimeters. Comparative Example 20
Wet-laid hand sheets were prepared using the following procedure. 7.5 gms of Albacel Southern Bleached Softwood Kraft (SBSK) from International Paper, Memphis, Tennessee, U.S.A. and 188 gms of room temperature water were placed in a 1000 ml pulper and pulped for 30 seconds at 7000 rpm to produce a pulped mixture. This pulped mixture was transferred into an 8 liter metal beaker along with 7312 gms of room temperature water to make about 0.1% consistency (7500 gms water and 7.5 gms fibrous material) pulp slurry. This pulp slurry was agitated using a high speed impeller mixer for 60 seconds. Procedure to make the hand sheet from this pulp slurry was as follows. The pulp slurry was poured into a 25 centimeters x 30 centimeters hand sheet mold while continuing to stir. The drop valve was pulled, and the pulp fibers were allowed to drain on a screen to form a hand sheet. 750 grams per square meter (gsm) blotter paper was placed on top of the formed hand sheet, and the blotter paper was flattened onto the hand sheet. The screen frame was raised and inverted onto a clean release paper and allowed to sit for 10 minutes. The screen was raised vertically away from the formed hand sheet. Two two sheets of 750 gsm blotter paper were placed on top of the formed hand sheet. The hand sheet was dried along with the three blotter papers using a Norwood Dryer at about 88°C for 15 minutes. One blotter paper was removed leaving one blotter paper on each side of the hand sheet. The hand sheet was dried using a Williams Dryer at 65°C for 15 minutes. The hand sheet was then further dried for 12 to 24 hours using a 40 kg dry press. The blotter paper was removed to obtain the dry hand sheet sample. The hand sheet was trimmed to 21.6 centimeters by 27.9 centimeters dimensions for testing.
Comparative Example 21
Wet-laid hand sheets were prepared using the following procedure. 7.5 gms of Albacel Southern Bleached Softwood Kraft (SBSK) from International Paper, Memphis, Tennessee, U.S.A., 0.3 gms of Solivitose N pre-gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands, and 188 gms of room temperature water were placed in a 1000 ml pulper and pulped for 30 seconds at 7000 rpm to produce a pulped mixture. This pulped mixture was transferred into an 8 liter metal beaker along with 7312 gms of room temperature water to make about 0.1% consistency (7500 gms water and 7.5 gms fibrous material) to produce a pulp slurry. This pulp slurry was agitated using a high speed impeller mixer for 60 seconds. The rest of procedure for making hand sheet from this pulp slurry was same as in Example 20.
Example 22
Wet-laid hand sheets were prepared using the following procedure. 6.0 gms of Albacel Southern Bleached Softwood Kraft (SBSK) from International Paper, Memphis, Tennessee, U.S.A., 0.3 gms of Solivitose N pre-gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands, 1.5 gms of 3.2 millimeter cut length islands-in-sea fibers of Example 16, and 188 gms of room temperature water were placed in a 1000 ml pulper and pulped for 30 seconds at 7000 rpm to produce a fiber mix slurry. This fiber mix slurry was heated to 82°C for 10 seconds to emulsify and remove the water dispersible sulfopolyester component in the islands-in-sea fibers and release polyester microfibers. The fiber mix slurry was then strained to produce a sulfopolyester dispersion comprising the sulfopolyester and a microfiber-containing mixture comprising pulp fibers and polyester microfiber. The microfiber-containing mixture was further rinsed using 500 gms of room temperature water to further remove the water dispersible sulfopolyester from the microfiber- containing mixture. This microfiber-containing mixture was transferred into an 8 liter metal beaker along with 7312 gms of room temperature water to make about 0.1% consistency (7500 gms water and 7.5 gms fibrous material) to produce a microfiber- containing slurry. This microfiber-containing slurry was agitated using a high speed impeller mixer for 60 seconds. The rest of procedure for making hand sheet from this microfiber-containing slurry was same as in Example 20. Comparative Example 23
Wet-laid hand sheets were prepared using the following procedure. 7.5 gms of MicroStrand 475-106 micro glass fiber available from Johns Manville, Denver, Colorado, U.S.A., 0.3 gms of Solivitose N pre-gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands, and 188 gms of room temperature water were placed in a 1000 ml pulper and pulped for 30 seconds at 7000 rpm to produce a glass fiber mixture. This glass fiber mixture was transferred into an 8 liter metal beaker along with 7312 gms of room temperature water to make about 0.1% consistency (7500 gms water and 7.5 gms fibrous material) to produce a glass fiber slurry. This glass fiber slurry was agitated using a high speed impeller mixer for 60 seconds. The rest of procedure for making hand sheet from this glass fiber slurry was same as in Example 20.
Example 24
Wet-laid hand sheets were prepared using the following procedure. 3.8 gms of MicroStrand 475-106 micro glass fiber available from Johns Manville, Denver, Colorado, U.S.A., 3.8 gms of 3.2 millimeter cut length islands-in-sea fibers of Example 16, 0.3 gms of Solivitose N pre-gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands, and 188 gms of room temperature water were placed in a 1000 ml pulper and pulped for 30 seconds at 7000 rpm to produce a fiber mix slurry. This fiber mix slurry was heated to 82°C for 10 seconds to emulsify and remove the water dispersible sulfopolyester component in the islands-in-sea bicomponent fibers and release polyester microfibers. The fiber mix slurry was then strained to produce a sulfopolyester dispersion comprising the sulfopolyester and a microfiber-containing mixture comprising glass microfibers and polyester microfiber. The microfiber-containing mixture was further rinsed using 500 gms of room temperature water to further remove the sulfopolyester from the microfiber-containing mixture. This microfiber-containing mixture was transferred into an 8 liter metal beaker along with 7312 gms of room temperature water to make about 0.1% consistency (7500 gms water and 7.5 gms fibrous material) to produce a microfiber- containing slurry. This microfϊber-containing slurry was agitated using a high speed impeller mixer for 60 seconds. The rest of procedure for making hand sheet from this microfiber-containing slurry was same as in Example 20.
Example 25
Wet-laid hand sheets were prepared using the following procedure. 7.5 gms of 3.2 millimeter cut length islands-in-sea fibers of Example 16, 0.3 gms of Solivitose N pre-gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands, and 188 gms of room temperature water were placed in a 1000 ml pulper and pulped for 30 seconds at 7000 rpm to produce a fiber mix slurry. This fiber mix slurry was heated to 82°C for 10 seconds to emulsify and remove the water dispersible sulfopolyester component in the islands-in-sea fibers and release polyester microfibers. The fiber mix slurry was then strained to produce a sulfopolyester dispersion and polyester microfibers. The sulfopolyester dispersion was comprised of water dispersible sulfopolyester. The polyester microfibers were rinsed using 500 gms of room temperature water to further remove the sulfopolyester from the polyester microfibers. These polyester microfibers were transferred into an 8 liter metal beaker along with 7312 gms of room temperature water to make about 0.1% consistency (7500 gms water and 7.5 gms fibrous material) to produce a microfiber slurry. This microfiber slurry was agitated using a high speed impeller mixer for 60 seconds. The rest of procedure for making hand sheet from this microfiber slurry was same as in Example 20.
The hand sheet samples of Examples 20-25 were tested and properties are provided in the following table.
Figure imgf000095_0001
The hand sheet basis weight was determined by weighing the hand sheet and calculating weight in grams per square meter (gsm). Hand sheet thickness was measured using an Ono Sokki EG-233 thickness gauge and reported as thickness in millimeters. Density was calculated as weight in grams per cubic centimeter. Porosity was measured using a Greiner Porosity Manometer with 1.9 x 1.9 cm square opening head and 100 cc capacity. Porosity is reported as average time in seconds (4 replicates) for 100 cc of water to pass through the sample. Tensile properties were measured using an Instron Model TM for six 30 mm x 105 mm test strips. An average of six measurements is reported for each example. It can be observed from these test data that significant improvement in tensile properties of wet-laid fibrous structures is obtained by the addition of polyester microfibers of the current invention.
Example 26
The sulfopolyester polymer of Example 13 was spun into bicomponent islands-in-the- sea cross-section fibers with 37 islands fibers using a bicomponent extrusion line. The primary extruder fed Eastman F61HC polyester to form the "islands" in the islands-in-the-sea cross-section structure. The secondary extruder fed the water dispersible sulfopolyester polymer to form the "sea" in the islands-in-sea bicomponent fiber. The inherent viscosity of the polyester was 0.61 dL/g while the melt viscosity of dry sulfopolyester was about 7000 poise measured at 240°C and 1 rad/sec strain rate using the melt viscosity measurement procedure described previously. These islands-in-sea bicomponent fibers were made using a spinneret with 72 holes and a throughput rate of 1.15gms/minute/hole. The polymer ratio between "islands" polyester and "sea" sulfopolyester was 2 to 1. These bicomponent fibers were spun using an extrusion temperature of 280°C for the polyester component and 255°C for the water dispersible sulfopolyester component. This bicomponent fiber contained a multiplicity of filaments (198 filaments) and was melt spun at a speed of about 530 meters/minute forming filaments with a nominal denier per filament of 19.5. A finish solution of 24% by weight PT 769 finish from Goulston Technologies was applied to the bicomponent fiber using a kiss roll applicator. The filaments of the bicomponent fiber were then drawn in line using a set of two godet rolls, heated to 95°C and 130°C respectively, and the final draw roll operating at a speed of about 1750 meters/minute, to provide a filament draw ratio of about 3.3X forming the drawn islands-in-sea bicomponent filaments with a nominal denier per filament of about 5.9 or an average diameter of about 29 microns. These filaments comprised the polyester microfiber islands of average diameter of about 3.9 microns.
Example 27
The drawn islands-in-sea bicomponent fibers of Example 26 were cut into short length bicomponent fibers of 3.2 millimeters and 6.4 millimeters cut length, thereby, producing short length fibers with 37 islands-in-sea cross-section configurations. These fibers comprised "islands" of polyester and "sea" of water dispersible sulfopolyester polymers. The cross-sectional distribution of "islands" and "sea" was essentially consistent along the length of these bicomponent fibers.
Example 28
The short cut length islands-in-sea fibers of Example 27 were washed using soft water at 80°C to remove the water dispersible sulfopolyester "sea" component, thereby, releasing the polyester microfibers which were the "islands" component of the bicomponent fibers. The washed polyester microfibers were rinsed using soft water at 25°C to essentially remove most of the "sea" component. The optical microscopic observation of the washed polyester microfibers had an average diameter of about 3.9 microns and lengths of 3.2 and 6.4 millimeters.
Example 29
The sulfopolyester polymer of Example 13 was spun into bicomponent islands-in-the- sea cross-section fibers with 37 islands fibers using a bicomponent extrusion line. The primary extruder fed polyester to form the "islands" in the islands-in-the-sea fiber cross-section structure. The secondary extruder fed the water dispersible sulfopolyester polymer to form the "sea" in the islands-in-sea bicomponent fiber. The inherent viscosity of the polyester was 0.52 dL/g while the melt viscosity of the dry water dispersible sulfopolyester was about 3500 poise measured at 240°C and 1 rad/sec strain rate using the melt viscosity measurement procedure described previously. These islands-in-sea bicomponent fibers were made using two spinnerets with 175 holes each and throughput rate of 1.0 gms/minute/hole. The polymer ratio between "islands" polyester and "sea" sulfopolyester was 70% to 30%. These bicomponent fibers were spun using an extrusion temperature of 280°C for the polyester component and 255°C for the sulfopolyester component. The bicomponent fibers contained a multiplicity of filaments (350 filaments) and were melt spun at a speed of about 1000 meters/minute using a take-up roll heated to 100°C forming filaments with a nominal denier per filament of about 9 and an average fiber diameter of about 36 microns. A finish solution of 24 wt% PT 769 finish was applied to the bicomponent fiber using a kiss roll applicator. The filaments of the bicomponent fiber were combined and were then drawn 3.0x on a draw line at draw roll speed of 100 m/minute and temperature of 38°C forming drawn islands-in-sea bicomponent filaments with an average denier per filament of about 3 and average diameter of about 20 microns. These drawn island-in-sea bicomponent fibers were cut into short length fibers of about 6.4 millimeters length. These short length islands-in-sea bicomponent fibers were comprised of polyester microfiber "islands" of average diameter of about 2.8 microns.
Example 30
The short cut length islands-in-sea bicomponent fibers of Example 29 were washed using soft water at 80°C to remove the water dispersible sulfopolyester "sea" component, thereby, releasing the polyester microfibers which were the "islands" component of the fibers. The washed polyester microfibers were rinsed using soft water at 25°C to essentially remove most of the "sea" component. The optical microscopic observation of washed fibers showed polyester microfibers of average diameter of about 2.8 microns and lengths of about 6.4 millimeters. Example 31
Wet-laid microfiber stock hand sheets were prepared using the following procedure. 56.3 gms of 3.2 millimeter cut length islands-in-sea bicomponent fibers of Example 16, 2.3 gms of Solivitose N pre-gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands, and 1410 gms of room temperature water were placed in a 2 liter beaker to produce a fiber slurry. The fiber slurry was stirred. One quarter amount of this fiber slurry, about 352 ml, was placed in 1000 ml pulper and pulped for 30 seconds at 7000 rpm. This fiber slurry was heated to 82°C for 10 seconds to emulsify and remove the water dispersible sulfopolyester component in the islands-in-sea bicomponent fibers and release polyester microfibers. The fiber slurry was then strained to produce a sulfopolyester dispersion and polyester microfibers. These polyester microfibers were rinsed using 500 gms of room temperature water to further remove the sulfopolyester from the polyester microfibers. Sufficient room temperature water was added to produce 352 ml of microfiber slurry. This microfiber slurry was re-pulped for 30 seconds at 7000 rpm. These microfibers were transferred into an 8 liter metal beaker. The remaining three quarters of the fiber slurry were similarly pulped, washed, rinsed and re-pulped and transferred to the 8 liter metal beaker. 6090 gms of room temperature water was then added to make about 0.49% consistency (7500 gms water and 36.6 gms of polyester microfibers) to produce a microfiber slurry. This microfiber slurry was agitated using a high speed impeller mixer for 60 seconds. The rest of procedure for making hand sheet from this microfiber slurry was same as in Example 20. The microfiber stock hand sheet with the basis weight of about 490 gsm was comprised of polyester microfibers of average diameter of about 2.5 microns and average length of about 3.2 millimeters. Example 32
Wet-laid hand sheets were prepared using the following procedure. 7.5 gms of polyester microfiber stock hand sheet of Example 31, 0.3 gms of Solivitose N pre- gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands, and 188 gms of room temperature water were placed in a 1000 ml pulper and pulped for 30 seconds at 7000 rpm. The microfibers were transferred into an 8 liter metal beaker along with 7312 gms of room temperature water to make about 0.1% consistency (7500 gms water and 7.5 gms fibrous material) to produce a microfiber slurry. This microfiber slurry was agitated using a high speed impeller mixer for 60 seconds. The rest of procedure for making hand sheet from this slurry was same as in Example 20. A 100 gsm wet-laid hand sheet of polyester microfibers was obtained having an average diameter of about 2.5 microns.
Example 33
The 6.4 millimeter cut length islands-in-sea bicomponent fibers of Example 29 were washed using soft water at 800C to remove the water dispersible sulfopolyester "sea" component, thereby, releasing the polyester microfibers which were the "islands" component of the bicomponent fibers. The washed polyester microfibers were rinsed using soft water at 25°C to essentially remove most of the "sea" component. The optical microscopic observation of the washed polyester microfibers showed an average diameter of about 2.5 microns and lengths of 6.4 millimeters.
Example 34
The short cut length islands-in-sea bicomponent fibers of Example 16, Example 27 and Example 29 were washed separately using soft water at 800C containing about 1% by weight based on the weight of the bicomponent fibers of ethylene diamine tetra acetic acid tetra sodium salt (Na4 EDTA) from Sigma-Aldrich Company, Atlanta, Georgia to remove the water dispersible sulfopolyester "sea" component, thereby, releasing the polyester microfibers which were the "islands" component of the bicomponent fibers. The addition of at least one water softener, such as Na4 EDTA, aids in the removal of the water dispersible sulfopolyester polymer from the islands- in-sea bicomponent fibers. The washed polyester microfibers were rinsed using soft water at 25°C to essentially remove most of the "sea" component. The optical microscopic observation of washed polyester microfibers showed excellent release and separation of polyester microfibers. Use of a water softing agent, such as Na4 EDTA in the water prevents any Ca4"1" ion exchange on the sulfopolyester which can adversely affect the water dispersiblity of sulfopolyester. Typical soft water may contain up to 15 ppm of Ca+"1" ion concentration. It is desirable that the soft water used in the processes described here should have essentially zero concentration of Ca+* and other multi-valent ions or alternately use sufficient amount of water softening agent, such as Na4 EDTA, to bind these Ca+* ions and other multi-valent ions. These polyester microfibers can be used in preparing the wet-laid sheets using the procedures of examples disclosed previously.
Example 35
The short cut length islands-in-sea bicomponent fibers of Example 16 and Example 27 were processed separately using the following procedure. 17 grams of Solivitose N pre-gelatinized quaternary cationic potato starch from Avebe, Foxhol, the Netherlands were added to the distilled water. After the starch was fully dissolved or hydrolyzed, then 429 grams of short cut length islands-in-sea bicomponent fibers were slowly added to the distilled water to produce a fiber slurry. A Williams Rotary Continuous Feed Refiner (5 inch diameter) was turned on to refine or mix the fiber slurry in order to provide sufficient shearing action for the water dispersible sulfopolyester to be separated from the polyester microfibers. The contents of the stock chest were poured into a 24 liter stainless steel container, and the lid was secured. The stainless steel container was placed on a propane cooker and heated until the fiber slurry began to boil at about 97°C in order to remove the sulfopolyester component in the island-in-sea fibers and release polyester microfibers. After the fiber slurry reached boiling, it was agitated with a manual agitating paddle. The contents of the stainless steel container were poured into a 27in x 15in x 6 in deep False Bottom Knuche with a 30 mesh screen to produce a sulfopolyester dispersion and polyester microfibers. The sulfopolyester dispersion comprised water and water dispersible sulfopolyester. The polyester microfibers were rinsed in the Knuche for 15 seconds with 10 liters of soft water at 17°C, and squeezed to remove excess water.
20 grams of polyester microfiber (dry fiber basis) was added to 2000ml of water at 70°C and agitated using a 2 liter 3000 rpm 3A horse power hydropulper manufactured by Hermann Manufacturing Company for 3 minutes (9,000 revolutions) to make a microfiber slurry of 1% consistency. Handsheets were made using the procedure described previously in Example 20.
The optical and scanning electron microscopic observation of these handsheets showed excellent separation and formation of polyester microfibers.

Claims

That which is claimed is:
1. A water non-dispersible polymer microfϊber comprising at least one water non-dispersible polymer wherein said water non-dispersible polymer microfiber has an equivalent diameter of less than 5 microns and length of less than 25 millimeters.
2. A water non-dispersible polymer microfϊber according to Claim 1 wherein said water non-dispersible polymer microfiber has an equivalent diameter of less than 3 microns and a length selected from the group consisting of less than 25 millimeters; less than 10 millimeters, less than 6.5 millimeters, and less than 3.5 millimeters.
3. A water non-dispersible polymer microfiber according to Claims 1 or 2 produced by the process comprising: a) providing a cut multicomponent fiber having a shaped cross section, said multicomponent fiber comprising:
At least one water dispersible sulfopolyester; and A plurality of microfiber domains comprising one or more water non- dispersible polymers immiscible with said sulfopolyester, wherein said microfiber domains are substantially isolated from each other by said sulfopolyester intervening between said microfiber domains; and b) separating the water non-dispersible polymer microfiber from said water dispersible sulfopolyester.
4. A water non-dispersible polymer microfiber according to Claim 3 wherein said multicomponent fiber has a shaped cross section, comprising:
(A) at least one water dispersible sulfopolyester; and
(B) a plurality of microfiber domains comprising one or more water non- dispersible polymers immiscible with the sulfopolyester, wherein the microfiber domains are substantially isolated from each other by the sulfopolyester intervening between the microfiber domains, wherein the water dispersible sulfopolyesters exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprises less than about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residues.
5. A water non-dispersible polymer microfiber according to Claim 3 wherein said multicomponent fiber has a shaped cross section, comprising:
(A) a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 570C, the sulfopolyester comprising:
(i) residues of one or more dicarboxylic acids;
(ii) about 4 to about 40 mole%, based on the total repeating units, of residues of at least one sulfomonomer having 2 functional groups and one or more sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
(iii) one or more diol residues wherein at least 25 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500; and
(iv) 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof; and
(B) a plurality of microfiber domains comprising one or more water non- dispersible polymers immiscible with the sulfopolyester, wherein the microfiber domains are substantially isolated from each/ other by the sulfopolyester intervening between the microfiber domains.
6. A water non-dispersible polymer microfiber according to Claim 3 wherein said multicomponent fiber has a shaped cross section, comprising:
(A) at least one water dispersible sulfopolyester; and
(B) a plurality of microfiber domains comprising one or more water non- dispersible polymers immiscible with the sulfopolyester, wherein the microfiber domains are substantially isolated from each other by the sulfopolyester intervening between the microfiber domains, wherein the fiber has an as-spun denier of less than about 6 denier per filament; and wherein the water dispersible sulfopolyesters exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprises less than about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residues.
7. A nonwoven article comprising said water non-dispersible polymer microfiber of Claims lor 2.
8. A nonwoven article of Claim 7 wherein said nonwoven article is produced by a dry-laid process or wet-laid process.
9. A nonwoven article of Claim 8 wherein at least 1% of said water non- dispersible polymer microfiber is contained in the nonwoven article.
10. A nonwoven article of Claim 8 where at least 25% of said water non- dispersible polymer microfiber is contained in the nonwoven article.
11. A nonwoven article of Claim 8 wherein at least 50% of said water non- dispersible polymer microfiber is contained in the nonwoven article.
12. A nonwoven article according to Claim 7 wherein said water non-dispersible polymer microfiber comprises at least one polymer selected from the group consisting of polyolefins, polyesters, polyamides, polylactides, polycaprolactone, polycarbonate, polyurethane, cellulose ester, and polyvinyl chloride.
13. A nonwoven article according to Claim 7 wherein said nonwoven article is an article selected from the group consisting of filter media, nonwoven fabrics, nonwoven webs, filter media for food preparation, filter media for medical applications, and paper.
14. A nonwoven article according to Claim 7 further comprising at least one other fiber.
15. A nonwoven article according to Claim 7 further comprising at least one additive.
16. A process for producing a nonwoven article said process comprising: a) providing a water non-dispersible polymer microfiber produced from a multicomponent fiber; b) producing said nonwoven article utilizing a wet-laid process or a dry-laid process.
17. A process according to Claim 16 wherein said multicomponent fiber is a multicomponent fiber having a shaped cross section, said multicomponent fiber comprising:
A) At least one water dispersible sulfopolyester; and
B) A plurality of microfiber domains comprising one or more water non- dispersible polymers immiscible with said sulfopolyester, wherein said microfiber domains are substantially isolated from each other by said sulfopolyester intervening between said microfiber domains.
18. A process according to Claim 16 wherein said multicomponent fiber has a shaped cross section, comprising:
(A) at least one water dispersible sulfopolyester; and
(B) a plurality of microfiber domains comprising one or more water non- dispersible polymers immiscible with the sulfopolyester, wherein the microfiber domains are substantially isolated from each other by the sulfopolyester intervening between the microfiber domains, wherein the water dispersible sulfopolyesters exhibits a melt viscosity of less than about 12,000 poise measured at 240°C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprises less than about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residues.
19. A process according to Claim 16 wherein said multicomponent fiber has a shaped cross section, comprising:
(A) a water dispersible sulfopolyester having a glass transition temperature (Tg) of at least 570C, the sulfopolyester comprising:
(i) residues of one or more dicarboxylic acids;
(ii) about 4 to about 40 mole%, based on the total repeating units, of residues of at least one sulfomonomer having 2 functional groups and one or more sulfonate groups attached to an aromatic or cycloaliphatic ring wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;
(iii) one or more diol residues wherein at least 25 mole%, based on the total diol residues, is a poly(ethylene glycol) having a structure
H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to about 500; and
(iv) 0 to about 25 mole%, based on the total repeating units, of residues of a branching monomer having 3 or more functional groups wherein the functional groups are hydroxyl, carboxyl, or a combination thereof; and
(B) a plurality of microfiber domains comprising one or more water non- dispersible polymers immiscible with the sulfopolyester, wherein the microfiber domains are substantially isolated from each other by the sulfopolyester intervening between the microfiber domains.
20. A process according to Claim 16 wherein said multicomponent fiber has a shaped cross section, comprising:
(A) at least one water dispersible sulfopolyester; and
(B) a plurality of microfiber domains comprising one or more water non- dispersible polymers immiscible with the sulfopolyester, wherein the microfiber domains are substantially isolated from each other by the sulfopolyester intervening between the microfiber domains, wherein the fiber has an as-spun denier of less than about 6 denier per filament; and wherein the water dispersible sulfopolyesters exhibits a melt viscosity of less than about 12,000 poise measured at 24O0C at a strain rate of 1 rad/sec, and wherein the sulfopolyester comprises less than about 25 mole % of residues of at least one sulfomonomer, based on the total moles of diacid or diol residues.
21. A process for producing water non-dispersible polymer microfibers, said process comprising: a) cutting a multicomponent fiber into cut multicomponent fibers; b) contacting a fiber-containing feedstock with water to produce a fiber mix slurry; wherein said fiber-containing feedstock comprises cut multicomponent fibers; c) heating said fiber mix slurry to produce a heated fiber mix slurry; d) optionally, mixing said fiber mix slurry in a shearing zone; e) removing at least a portion of the sulfopolyester from said multicomponent fiber to produce a slurry mixture comprising a sulfopolyester dispersion and water non-dispersible polymer microfibers; and f) separating said water non-dispersible polymer microfibers from said slurry mixture.
22. A process according to Claim 21 wherein said water non-dispersible polymer microfibers are utilized in a wet-laid process or dry-laid process.
23. A process according to Claim 21 wherein said water non-dispersible polymer microfibers slurry further comprises at least one fiber selected from the group consisting of cellulosic fiber pulp, glass fiber, polyester fibers, nylon fibers, polyolefin fibers, rayon fibers and cellulose ester fibers.
24. A process according to Claim 21 wherein step 16 b said water comprises at least one water softening agent.
25. A process accordint to Claim 21 wherein said water softening agent is a chelating agent or calcium ion sequestrant.
26. A process according to Claim 25 wherein said water softening agent is selected from the group consisting of poly acrylic acid sodium salt; sodium salts of maleic acid or succinic acid; diethylenetriaminepentaacetic acid; diethylenetriamine- N,N,N',N',N"-pentaacetic acid; pentetic acid; N,N-bis(2-(bis- (carboxymethyl)amino)ethyl)-glycine; diethylenetriamine pentaacetic acid; [[(carboxymethyl)imino]bis(ethylenenitrilo)]-tetra-acetic acid; edetic acid; ethylenedinitrilotetraacetic acid; EDTA, free base; EDTA free acid; ethylenediamine- N,N,N',N'-tetraacetic acid; hampene; versene; N,N'-l,2-ethane diylbis-(N- (carboxymethyl)glycine); ethylenediamine tetra-acetic acid; N5N- bis(carboxymethyl)glycine; triglycollamic acid; trilone A; alpha,alpha',alpha"- trimethylaminetricarboxylic acid; tri(carboxymethyl)amine; aminotriacetic acid; hampshire NTA acid; nitrilo-2,2',2"-triacetic acid; titriplex i; nitrilotriacetic acid; and mixtures thereof.
27. A wet-laid process to produce a nonwoven article, said wet-laid process comprising: a) optionally, rinsing said water non-dispersible polymer microfibers; b) adding water to said water non-dispersible polymer microfibers to produce a water non-dispersible polymer microfiber slurry; c) optionally, adding other fibers and /or additives to said water non- dispersible polymer microfϊbers or water non-dispersible polymer microfiber slurry; and d) transferring said water non-dispersible polymer microfiber containing slurry to a wet-laid nonwoven zone to produce said nonwoven article.
PCT/US2009/001717 2008-04-02 2009-03-19 Nonwovens produced from multicomponent fibers WO2009123678A1 (en)

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DK09727198T DK2271797T3 (en) 2008-04-02 2009-03-19 Nonwoven fabric made from multi-component fibers
BRPI0909456A BRPI0909456A2 (en) 2008-04-02 2009-03-19 non-water dispersible polymeric microfiber, nonwoven article, and process for producing a nonwoven article for producing non-water dispersible polymeric microfibers, and wet deposition.
KR1020107024652A KR101362617B1 (en) 2008-04-02 2009-03-19 Nonwovens produced from multicomponent fibers
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013540212A (en) * 2010-10-21 2013-10-31 イーストマン ケミカル カンパニー Wet wrap compositions and related methods
JP2013544976A (en) * 2010-10-21 2013-12-19 イーストマン ケミカル カンパニー Nonwoven products with ribbon fibers
JP2014511947A (en) * 2011-04-07 2014-05-19 イーストマン ケミカル カンパニー Short cut microfiber
EP2809412A4 (en) * 2012-01-31 2016-03-09 Eastman Chem Co Processes to produce short cut microfibers

Families Citing this family (89)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8513147B2 (en) 2003-06-19 2013-08-20 Eastman Chemical Company Nonwovens produced from multicomponent fibers
US20040260034A1 (en) 2003-06-19 2004-12-23 Haile William Alston Water-dispersible fibers and fibrous articles
US7892993B2 (en) 2003-06-19 2011-02-22 Eastman Chemical Company Water-dispersible and multicomponent fibers from sulfopolyesters
US20120251597A1 (en) * 2003-06-19 2012-10-04 Eastman Chemical Company End products incorporating short-cut microfibers
US8540846B2 (en) 2009-01-28 2013-09-24 Georgia-Pacific Consumer Products Lp Belt-creped, variable local basis weight multi-ply sheet with cellulose microfiber prepared with perforated polymeric belt
US9498932B2 (en) 2008-09-30 2016-11-22 Exxonmobil Chemical Patents Inc. Multi-layered meltblown composite and methods for making same
US8664129B2 (en) 2008-11-14 2014-03-04 Exxonmobil Chemical Patents Inc. Extensible nonwoven facing layer for elastic multilayer fabrics
US9168718B2 (en) 2009-04-21 2015-10-27 Exxonmobil Chemical Patents Inc. Method for producing temperature resistant nonwovens
US10161063B2 (en) 2008-09-30 2018-12-25 Exxonmobil Chemical Patents Inc. Polyolefin-based elastic meltblown fabrics
DE102009051105A1 (en) * 2008-10-31 2010-05-12 Mann+Hummel Gmbh Nonwoven medium, process for its preparation and made of this filter element
KR101348060B1 (en) 2009-02-27 2014-01-03 엑손모빌 케미칼 패턴츠 인코포레이티드 Multi-layer nonwoven in situ laminates and method of producing the same
US8950587B2 (en) 2009-04-03 2015-02-10 Hollingsworth & Vose Company Filter media suitable for hydraulic applications
US20100272938A1 (en) 2009-04-22 2010-10-28 Bemis Company, Inc. Hydraulically-Formed Nonwoven Sheet with Microfibers
US8512519B2 (en) * 2009-04-24 2013-08-20 Eastman Chemical Company Sulfopolyesters for paper strength and process
US8668975B2 (en) 2009-11-24 2014-03-11 Exxonmobil Chemical Patents Inc. Fabric with discrete elastic and plastic regions and method for making same
US8889572B2 (en) 2010-09-29 2014-11-18 Milliken & Company Gradient nanofiber non-woven
US8795561B2 (en) 2010-09-29 2014-08-05 Milliken & Company Process of forming a nanofiber non-woven containing particles
DE102010048407A1 (en) * 2010-10-15 2012-04-19 Carl Freudenberg Kg Hydrogelierende fibers and fiber structures
US20120184164A1 (en) * 2010-10-21 2012-07-19 Eastman Chemical Company Paperboard or cardboard
WO2012054671A1 (en) * 2010-10-21 2012-04-26 Eastman Chemical Company Sulfopolyester binders
US20120183861A1 (en) * 2010-10-21 2012-07-19 Eastman Chemical Company Sulfopolyester binders
US20120183862A1 (en) * 2010-10-21 2012-07-19 Eastman Chemical Company Battery separator
US20120219766A1 (en) * 2010-10-21 2012-08-30 Eastman Chemical Company High strength specialty paper
US20120175298A1 (en) * 2010-10-21 2012-07-12 Eastman Chemical Company High efficiency filter
US20120302119A1 (en) * 2011-04-07 2012-11-29 Eastman Chemical Company Short cut microfibers
US9096955B2 (en) 2011-09-30 2015-08-04 Ut-Battelle, Llc Method for the preparation of carbon fiber from polyolefin fiber precursor, and carbon fibers made thereby
US20130123409A1 (en) * 2011-11-11 2013-05-16 Eastman Chemical Company Solvent-borne products containing short-cut microfibers
US8906200B2 (en) 2012-01-31 2014-12-09 Eastman Chemical Company Processes to produce short cut microfibers
US9096959B2 (en) 2012-02-22 2015-08-04 Ut-Battelle, Llc Method for production of carbon nanofiber mat or carbon paper
US9662600B2 (en) 2012-03-09 2017-05-30 Ahlstrom Corporation High efficiency and high capacity glass-free fuel filtration media and fuel filters and methods employing the same
US10357729B2 (en) 2012-03-09 2019-07-23 Ahlstrom-Munksjö Oyj High efficiency and high capacity glass-free fuel filtration media and fuel filters and methods employing the same
US9353480B2 (en) 2012-04-11 2016-05-31 Ahlstrom Corporation Sterilizable and printable nonwoven packaging materials
KR101341055B1 (en) * 2012-12-26 2013-12-13 박희대 The method of preparing a thermoplastic polyurethane yarn
US10421033B2 (en) 2013-03-09 2019-09-24 Donaldson Company, Inc. Nonwoven filtration media including microfibrillated cellulose fibers
FR3003581B1 (en) 2013-03-20 2015-03-20 Ahlstroem Oy FIBROUS MEDIUM BASED ON FIBERS AND NANOFIBRILS OF POLYSACCHARIDE
FR3003580B1 (en) 2013-03-20 2015-07-03 Ahlstroem Oy WET-NON-WOVEN COMPRISING CELLULOSE NANOFIBRILLES
US9303357B2 (en) 2013-04-19 2016-04-05 Eastman Chemical Company Paper and nonwoven articles comprising synthetic microfiber binders
WO2014192746A1 (en) * 2013-05-30 2014-12-04 帝人株式会社 Organic resin non-crimped staple fiber
US9605126B2 (en) 2013-12-17 2017-03-28 Eastman Chemical Company Ultrafiltration process for the recovery of concentrated sulfopolyester dispersion
US9598802B2 (en) 2013-12-17 2017-03-21 Eastman Chemical Company Ultrafiltration process for producing a sulfopolyester concentrate
US10744435B2 (en) * 2014-07-30 2020-08-18 Sabic Global Technologies B.V. Spunbond polycarbonate resin filter media
US11292909B2 (en) 2014-12-19 2022-04-05 Earth Renewable Technologies Extrudable polymer composition and method of making molded articles utilizing the same
US9738752B2 (en) * 2015-04-24 2017-08-22 Xerox Corporation Copolymers for 3D printing
CN105696105A (en) * 2016-03-23 2016-06-22 太仓市洪宇新材料科技有限公司 Preparation technology of normal temperature and pressure dyeable PBT (polybutylece terephthalate) fiber
GB2569081B (en) 2016-09-29 2021-08-04 Kimberly Clark Co Soft tissue comprising synthetic fibers
CN106541685A (en) * 2016-11-03 2017-03-29 李素英 A kind of cloth production method and cloth
US10450703B2 (en) 2017-02-22 2019-10-22 Kimberly-Clark Worldwide, Inc. Soft tissue comprising synthetic fibers
WO2018193165A1 (en) 2017-04-21 2018-10-25 Ahlstrom-Munksjö Oyj Filter units provided with high-efficiency and high capacity glass-free fuel filtration media
JP6997583B2 (en) * 2017-10-19 2022-01-17 日本フイルコン株式会社 Mesh belt used in water absorber manufacturing equipment
CN109943980B (en) * 2017-12-20 2021-02-23 财团法人纺织产业综合研究所 Non-woven fabric structure and manufacturing method thereof
JP7013486B2 (en) * 2018-01-24 2022-01-31 三井化学株式会社 Manufacturing method of spunbonded non-woven fabric, sanitary material, and spunbonded non-woven fabric
US11466408B2 (en) 2018-08-23 2022-10-11 Eastman Chemical Company Highly absorbent articles
US11408128B2 (en) 2018-08-23 2022-08-09 Eastman Chemical Company Sheet with high sizing acceptance
US11441267B2 (en) 2018-08-23 2022-09-13 Eastman Chemical Company Refining to a desirable freeness
US11479919B2 (en) * 2018-08-23 2022-10-25 Eastman Chemical Company Molded articles from a fiber slurry
US11414818B2 (en) 2018-08-23 2022-08-16 Eastman Chemical Company Dewatering in paper making process
US11639579B2 (en) 2018-08-23 2023-05-02 Eastman Chemical Company Recycle pulp comprising cellulose acetate
US11519132B2 (en) 2018-08-23 2022-12-06 Eastman Chemical Company Composition of matter in stock preparation zone of wet laid process
US11390996B2 (en) 2018-08-23 2022-07-19 Eastman Chemical Company Elongated tubular articles from wet-laid webs
US11492756B2 (en) 2018-08-23 2022-11-08 Eastman Chemical Company Paper press process with high hydrolic pressure
US11421387B2 (en) 2018-08-23 2022-08-23 Eastman Chemical Company Tissue product comprising cellulose acetate
US11306433B2 (en) 2018-08-23 2022-04-19 Eastman Chemical Company Composition of matter effluent from refiner of a wet laid process
US11512433B2 (en) 2018-08-23 2022-11-29 Eastman Chemical Company Composition of matter feed to a head box
US11420784B2 (en) 2018-08-23 2022-08-23 Eastman Chemical Company Food packaging articles
US11525215B2 (en) 2018-08-23 2022-12-13 Eastman Chemical Company Cellulose and cellulose ester film
US11286619B2 (en) 2018-08-23 2022-03-29 Eastman Chemical Company Bale of virgin cellulose and cellulose ester
US11390991B2 (en) 2018-08-23 2022-07-19 Eastman Chemical Company Addition of cellulose esters to a paper mill without substantial modifications
US11230811B2 (en) 2018-08-23 2022-01-25 Eastman Chemical Company Recycle bale comprising cellulose ester
US11396726B2 (en) 2018-08-23 2022-07-26 Eastman Chemical Company Air filtration articles
US11530516B2 (en) 2018-08-23 2022-12-20 Eastman Chemical Company Composition of matter in a pre-refiner blend zone
US11401660B2 (en) 2018-08-23 2022-08-02 Eastman Chemical Company Broke composition of matter
US11421385B2 (en) 2018-08-23 2022-08-23 Eastman Chemical Company Soft wipe comprising cellulose acetate
US11332885B2 (en) 2018-08-23 2022-05-17 Eastman Chemical Company Water removal between wire and wet press of a paper mill process
US11401659B2 (en) 2018-08-23 2022-08-02 Eastman Chemical Company Process to produce a paper article comprising cellulose fibers and a staple fiber
US11313081B2 (en) 2018-08-23 2022-04-26 Eastman Chemical Company Beverage filtration article
US11414791B2 (en) 2018-08-23 2022-08-16 Eastman Chemical Company Recycled deinked sheet articles
US11339537B2 (en) 2018-08-23 2022-05-24 Eastman Chemical Company Paper bag
US11299854B2 (en) 2018-08-23 2022-04-12 Eastman Chemical Company Paper product articles
US11492755B2 (en) * 2018-08-23 2022-11-08 Eastman Chemical Company Waste recycle composition
US11332888B2 (en) * 2018-08-23 2022-05-17 Eastman Chemical Company Paper composition cellulose and cellulose ester for improved texturing
US11492757B2 (en) 2018-08-23 2022-11-08 Eastman Chemical Company Composition of matter in a post-refiner blend zone
CN109603313B (en) * 2018-12-14 2021-05-07 核工业理化工程研究院 Preparation method of adsorption filter element for treating radioactive waste liquid and adsorption filter element
US11408098B2 (en) * 2019-03-22 2022-08-09 Global Materials Development, LLC Methods for producing polymer fibers and polymer fiber products from multicomponent fibers
AR118565A1 (en) * 2019-04-16 2021-10-20 Dow Global Technologies Llc BICOMPONENT FIBERS, NON-WOVEN NETS AND PROCESSES TO ELABORATE THEM
CN114846187A (en) * 2019-09-30 2022-08-02 蒙诺苏尔有限公司 Water-soluble nonwoven webs for packaging harsh chemicals
US11215752B1 (en) 2019-12-13 2022-01-04 Apple Inc. Electronic devices with image transport layers
CN111575831B (en) * 2020-05-19 2022-12-16 浙江恒逸石化研究院有限公司 Preparation method of water-repellent anti-fouling low-melting-point composite fiber
KR20230125191A (en) 2020-11-10 2023-08-29 네나 게쓰너 게엠바하 Filter media comprising non-woven electrets
CN113549289A (en) * 2021-07-22 2021-10-26 浙江佰利眼镜有限公司 Reinforced compound of polyvinylidene fluoride

Citations (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3018272A (en) 1955-06-30 1962-01-23 Du Pont Sulfonate containing polyesters dyeable with basic dyes
US3033822A (en) 1959-06-29 1962-05-08 Eastman Kodak Co Linear polyesters of 1, 4-cyclohexane-dimethanol and hydroxycarboxylic acids
US3075952A (en) 1959-01-21 1963-01-29 Eastman Kodak Co Solid phase process for linear superpolyesters
US3528947A (en) 1968-01-03 1970-09-15 Eastman Kodak Co Dyeable polyesters containing units of an alkali metal salts of an aromatic sulfonic acid or ester thereof
US3779993A (en) 1970-02-27 1973-12-18 Eastman Kodak Co Polyesters and polyesteramides containing ether groups and sulfonate groups in the form of a metallic salt
US4304901A (en) 1980-04-28 1981-12-08 Eastman Kodak Company Water dissipatable polyesters
US4966808A (en) 1989-01-27 1990-10-30 Chisso Corporation Micro-fibers-generating conjugate fibers and woven or non-woven fabric thereof
US5281306A (en) 1988-11-30 1994-01-25 Kao Corporation Water-disintegrable cleaning sheet
US5290631A (en) 1991-10-29 1994-03-01 Rhone-Poulenc Chimie Hydrosoluble/hydrodispersible polyesters and sizing of textile threads therewith
US5292581A (en) 1992-12-15 1994-03-08 The Dexter Corporation Wet wipe
US5366804A (en) 1993-03-31 1994-11-22 Basf Corporation Composite fiber and microfibers made therefrom
US5405698A (en) 1993-03-31 1995-04-11 Basf Corporation Composite fiber and polyolefin microfibers made therefrom
US5486418A (en) 1993-10-15 1996-01-23 Kuraray Co., Ltd. Water-soluble heat-press-bonding polyvinyl alcohol binder fiber of a sea-islands structure
US5509913A (en) 1993-12-16 1996-04-23 Kimberly-Clark Corporation Flushable compositions
US5543488A (en) 1994-07-29 1996-08-06 Eastman Chemical Company Water-dispersible adhesive composition and process
US5570605A (en) 1994-09-13 1996-11-05 Kanzaki Kokyukoki Mfg. Co., Ltd. Transmission assembly for tractors
US5853701A (en) 1993-06-25 1998-12-29 George; Scott E. Clear aerosol hair spray formulations containing a sulfopolyester in a hydroalcoholic liquid vehicle
US5916678A (en) 1995-06-30 1999-06-29 Kimberly-Clark Worldwide, Inc. Water-degradable multicomponent fibers and nonwovens
US5935880A (en) 1997-03-31 1999-08-10 Wang; Kenneth Y. Dispersible nonwoven fabric and method of making same
US6171685B1 (en) 1999-11-26 2001-01-09 Eastman Chemical Company Water-dispersible films and fibers based on sulfopolyesters
US6211309B1 (en) 1998-06-29 2001-04-03 Basf Corporation Water-dispersable materials
WO2001066666A2 (en) 2000-03-09 2001-09-13 Ato Findley, Inc. Sulfonated copolyester based water-dispersible hot melt adhesive
US6548592B1 (en) 2000-05-04 2003-04-15 Kimberly-Clark Worldwide, Inc. Ion-sensitive, water-dispersible polymers, a method of making same and items using same
US6552162B1 (en) 1997-07-31 2003-04-22 Kimberly-Clark Worldwide, Inc. Water-responsive, biodegradable compositions and films and articles comprising a blend of polylactide and polyvinyl alcohol and methods for making the same
WO2007089423A2 (en) 2006-01-31 2007-08-09 Eastman Chemical Company Water-dispersible and multicomponent fibers from sulfopolyesters
WO2008085332A2 (en) * 2007-01-03 2008-07-17 Eastman Chemical Company Nonwovens fabrics produced from multicomponent fibers comprising sulfopolyesters

Family Cites Families (627)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US792343A (en) * 1897-12-31 1905-06-13 Gen Fire Extinguisher Co Automatic sprinkler.
US3049469A (en) 1957-11-07 1962-08-14 Hercules Powder Co Ltd Application of coating or impregnating materials to fibrous material
US1814155A (en) 1930-05-16 1931-07-14 Theodore P Haughey Process of treating vegetable fibers
US2862251A (en) 1955-04-12 1958-12-02 Chicopee Mfg Corp Method of and apparatus for producing nonwoven product
NL246230A (en) 1958-12-09
GB1073640A (en) 1963-11-22 1967-06-28 Goodyear Tire & Rubber Method for preparing copolyesters
US3556932A (en) 1965-07-12 1971-01-19 American Cyanamid Co Water-soluble,ionic,glyoxylated,vinylamide,wet-strength resin and paper made therewith
US3531368A (en) 1966-01-07 1970-09-29 Toray Industries Synthetic filaments and the like
US3372084A (en) 1966-07-18 1968-03-05 Mead Corp Post-formable absorbent paper
US3485706A (en) 1968-01-18 1969-12-23 Du Pont Textile-like patterned nonwoven fabrics and their production
US3592796A (en) 1969-03-10 1971-07-13 Celanese Corp Linear polyester polymers containing alkali metal salts of sulfonated aliphatic compounds
US3783093A (en) 1969-05-01 1974-01-01 American Cyanamid Co Fibrous polyethylene materials
US3772076A (en) 1970-01-26 1973-11-13 Hercules Inc Reaction products of epihalohydrin and polymers of diallylamine and their use in paper
US3833457A (en) 1970-03-20 1974-09-03 Asahi Chemical Ind Polymeric complex composite
CS155307B1 (en) 1970-06-01 1974-05-30
US3846507A (en) 1972-04-06 1974-11-05 Union Carbide Canada Ltd Polyamide blends with one polyamide containing phthalate sulfonate moieties and terphthalate on isophthalate residues
US4008344A (en) 1973-04-05 1977-02-15 Toray Industries, Inc. Multi-component fiber, the method for making said and polyurethane matrix sheets formed from said
US4073988A (en) 1974-02-08 1978-02-14 Kanebo, Ltd. Suede-like artificial leathers and a method for manufacturing same
US4100324A (en) 1974-03-26 1978-07-11 Kimberly-Clark Corporation Nonwoven fabric and method of producing same
US3998740A (en) 1974-07-26 1976-12-21 J. P. Stevens & Co., Inc. Apparatus for treatment of textile desizing effluent
US4073777A (en) 1975-01-17 1978-02-14 Eastman Kodak Company Radiation crosslinkable polyester and polyesteramide compositions containing sulfonate groups in the form of a metallic salt and unsaturated groups
US4121966A (en) 1975-02-13 1978-10-24 Mitsubishi Paper Mills, Ltd. Method for producing fibrous sheet
DE2516305A1 (en) 1975-04-15 1976-10-28 Dynamit Nobel Ag WATER DISPENSABLE ESTER RESINS
GB1556710A (en) 1975-09-12 1979-11-28 Anic Spa Method of occluding substances in structures and products obtained thereby
JPS52155269A (en) 1976-06-17 1977-12-23 Toray Industries Suedeelike textile and method of producing same
US4137393A (en) 1977-04-07 1979-01-30 Monsanto Company Polyester polymer recovery from dyed polyester fibers
US4226672A (en) 1977-07-01 1980-10-07 Ici Australia Limited Process of separating asbestos fibers and product thereof
CH632546A5 (en) 1977-08-26 1982-10-15 Ciba Geigy Ag METHOD FOR PRODUCING SIZED PAPER OR CARDBOARD USING POLYELECTROLYTE AND SALTS OF EPOXYD-AMINE-POLYAMINOAMIDE IMPLEMENTATION PRODUCTS.
US4145469A (en) 1977-10-11 1979-03-20 Basf Wyandotte Corporation Water-insoluble treated textile and processes therefor
US4243480A (en) 1977-10-17 1981-01-06 National Starch And Chemical Corporation Process for the production of paper containing starch fibers and the paper produced thereby
FR2407980A1 (en) 1977-11-02 1979-06-01 Rhone Poulenc Ind NEW ANTI-SOILING AND ANTI-REDEPOSITION COMPOSITIONS FOR USE IN DETERGENCE
US4239720A (en) 1978-03-03 1980-12-16 Akzona Incorporated Fiber structures of split multicomponent fibers and process therefor
US4233355A (en) 1978-03-09 1980-11-11 Toray Industries, Inc. Separable composite fiber and process for producing same
US4288503A (en) 1978-06-16 1981-09-08 Amerace Corporation Laminated microporous article
US4288508A (en) 1978-09-18 1981-09-08 University Patents, Inc. Chalcogenide electrochemical cell
FR2442901A1 (en) 1978-11-30 1980-06-27 Rhone Poulenc Textile DOUBLE CONSTITUENT ACRYLIC FIBERS
US4381335A (en) 1979-11-05 1983-04-26 Toray Industries, Inc. Multi-component composite filament
DE2951307A1 (en) 1979-12-20 1981-07-02 Akzo Gmbh, 5600 Wuppertal SUEDE-LIKE AREA
CA1149985A (en) 1980-04-26 1983-07-12 Takashi Okamoto Resin composition comprising water-soluble polyamide and vinyl alcohol-based polymer
US4302495A (en) 1980-08-14 1981-11-24 Hercules Incorporated Nonwoven fabric of netting and thermoplastic polymeric microfibers
US4496619A (en) 1981-04-01 1985-01-29 Toray Industries, Inc. Fabric composed of bundles of superfine filaments
US4427557A (en) 1981-05-14 1984-01-24 Ici Americas Inc. Anionic textile treating compositions
KR830002440B1 (en) 1981-09-05 1983-10-26 주식회사 코오롱 Composite fiber
JPS58174625A (en) 1982-04-06 1983-10-13 Teijin Ltd Binder fiber
CA1234519A (en) 1982-04-13 1988-03-29 Shusuke Yoshida Chenille woven or knitted fabric and process for producing the same
US4410579A (en) 1982-09-24 1983-10-18 E. I. Du Pont De Nemours And Company Nonwoven fabric of ribbon-shaped polyester fibers
JPS5962050A (en) 1982-09-30 1984-04-09 日本バイリ−ン株式会社 Skin adhering agent
US4480085A (en) * 1983-09-30 1984-10-30 Minnesota Mining And Manufacturing Company Amorphous sulfopolyesters
US4795668A (en) 1983-10-11 1989-01-03 Minnesota Mining And Manufacturing Company Bicomponent fibers and webs made therefrom
JPS6120741A (en) 1984-07-09 1986-01-29 東レ株式会社 Easily adhesive polyester film
DE3437183C2 (en) 1984-10-10 1986-09-11 Fa. Carl Freudenberg, 6940 Weinheim Microporous multilayer nonwoven for medical purposes and processes for the production thereof
US4647497A (en) 1985-06-07 1987-03-03 E. I. Du Pont De Nemours And Company Composite nonwoven sheet
NZ217669A (en) 1985-10-02 1990-03-27 Surgikos Inc Meltblown microfibre web includes core web and surface veneer
US4873273A (en) 1986-03-20 1989-10-10 James River-Norwalk, Inc. Epoxide coating composition
US4738785A (en) 1987-02-13 1988-04-19 Eastman Kodak Company Waste treatment process for printing operations employing water dispersible inks
JPS63227898A (en) 1987-03-12 1988-09-22 帝人株式会社 Wet nonwoven fabric
DE3708916A1 (en) 1987-03-19 1988-09-29 Boehringer Ingelheim Kg METHOD FOR CLEANING RESORBABLE POLYESTERS
US5242640A (en) 1987-04-03 1993-09-07 E. I. Du Pont De Nemours And Company Preparing cationic-dyeable textured yarns
US4755421A (en) 1987-08-07 1988-07-05 James River Corporation Of Virginia Hydroentangled disintegratable fabric
US5162074A (en) 1987-10-02 1992-11-10 Basf Corporation Method of making plural component fibers
US4804719A (en) 1988-02-05 1989-02-14 Eastman Kodak Company Water-dissipatable polyester and polyester-amides containing copolymerized colorants
US4940744A (en) 1988-03-21 1990-07-10 Eastman Kodak Company Insolubilizing system for water based inks
DK245488D0 (en) 1988-05-05 1988-05-05 Danaklon As SYNTHETIC FIBER AND PROCEDURES FOR PRODUCING THEREOF
US5039339A (en) 1988-07-28 1991-08-13 Eastman Kodak Company Ink composition containing a blend of a polyester and an acrylic polymer
US4996252A (en) 1988-07-28 1991-02-26 Eastman Kodak Company Ink composition containing a blend of a polyester and an acrylic polymer
US5262460A (en) 1988-08-04 1993-11-16 Teijin Limited Aromatic polyester resin composition and fiber
US4943477A (en) 1988-09-27 1990-07-24 Mitsubishi Rayon Co., Ltd. Conductive sheet having electromagnetic interference shielding function
US5338406A (en) 1988-10-03 1994-08-16 Hercules Incorporated Dry strength additive for paper
US4921899A (en) 1988-10-11 1990-05-01 Eastman Kodak Company Ink composition containing a blend of a polyester, an acrylic polymer and a vinyl polymer
US4910292A (en) 1988-10-14 1990-03-20 Eastman Kodak Company Water-dissipatable polyester resins and coatings prepared therefrom
US4990593A (en) 1988-10-14 1991-02-05 Eastman Kodak Company Water-dissipatable polyester resins and coatings prepared therefrom
US5416156A (en) 1988-10-14 1995-05-16 Revlon Consumer Products Corporation Surface coating compositions containing fibrillated polymer
US4863785A (en) 1988-11-18 1989-09-05 The James River Corporation Nonwoven continuously-bonded trilaminate
US4946932A (en) 1988-12-05 1990-08-07 Eastman Kodak Company Water-dispersible polyester blends
US5069970A (en) 1989-01-23 1991-12-03 Allied-Signal Inc. Fibers and filters containing said fibers
US5296286A (en) 1989-02-01 1994-03-22 E. I. Du Pont De Nemours And Company Process for preparing subdenier fibers, pulp-like short fibers, fibrids, rovings and mats from isotropic polymer solutions
JP2682130B2 (en) 1989-04-25 1997-11-26 三井石油化学工業株式会社 Flexible long-fiber non-woven fabric
JP2783602B2 (en) 1989-07-19 1998-08-06 チッソ株式会社 Ultrafine composite fiber for thermal bonding and its woven or nonwoven fabric
US5073436A (en) 1989-09-25 1991-12-17 Amoco Corporation Multi-layer composite nonwoven fabrics
FR2654674A1 (en) 1989-11-23 1991-05-24 Rhone Poulenc Films Anti-blocking composite polyester films
US5057368A (en) 1989-12-21 1991-10-15 Allied-Signal Filaments having trilobal or quadrilobal cross-sections
FI112252B (en) 1990-02-05 2003-11-14 Fibervisions L P High temperature resistant fiber bindings
US5006598A (en) 1990-04-24 1991-04-09 Eastman Kodak Company Water-dispersible polyesters imparting improved water resistance properties to inks
US5171309A (en) 1990-05-11 1992-12-15 E. I. Du Pont De Nemours And Company Polyesters and their use in compostable products such as disposable diapers
FR2667622B1 (en) 1990-10-08 1994-10-07 Kaysersberg Sa HYDRAULICALLY LINKED MONTISSE AND MANUFACTURING METHOD THEREOF.
JPH04189840A (en) 1990-11-22 1992-07-08 Jsp Corp Production of foamed polymer particle
SG47853A1 (en) 1990-11-30 1998-04-17 Eastman Chem Co Aliphatic-aromatic copolyesters and cellulose ester/polymer blend
US5162399A (en) 1991-01-09 1992-11-10 Eastman Kodak Company Ink millbase and method for preparation thereof
US5290626A (en) 1991-02-07 1994-03-01 Chisso Corporation Microfibers-generating fibers and a woven or non-woven fabric of microfibers
US5158844A (en) 1991-03-07 1992-10-27 The Dexter Corporation Battery separator
JP2912472B2 (en) 1991-04-24 1999-06-28 鐘紡株式会社 Water soluble fiber
US5171767A (en) 1991-05-06 1992-12-15 Rohm And Haas Company Utrafiltration process for the recovery of polymeric latices from whitewater
EP0548364A4 (en) 1991-05-14 1994-06-22 Kanebo Ltd Potentially elastic conjugate fiber, production thereof, and production of fibrous structure with elasticity in expansion and contraction
US5340581A (en) 1991-08-23 1994-08-23 Gillette Canada, Inc. Sustained-release matrices for dental application
US5218042A (en) 1991-09-25 1993-06-08 Thauming Kuo Water-dispersible polyester resins and process for their preparation
US5176952A (en) 1991-09-30 1993-01-05 Minnesota Mining And Manufacturing Company Modulus nonwoven webs based on multi-layer blown microfibers
US5258220A (en) 1991-09-30 1993-11-02 Minnesota Mining And Manufacturing Company Wipe materials based on multi-layer blown microfibers
US5277976A (en) 1991-10-07 1994-01-11 Minnesota Mining And Manufacturing Company Oriented profile fibers
US5503907A (en) 1993-07-19 1996-04-02 Fiberweb North America, Inc. Barrier fabrics which incorporate multicomponent fiber support webs
JP2695557B2 (en) * 1991-12-16 1997-12-24 株式会社クラレ Copolyester, production method thereof and use of the copolyester
US5318669A (en) 1991-12-23 1994-06-07 Hercules Incorporated Enhancement of paper dry strength by anionic and cationic polymer combination
US5545481A (en) 1992-02-14 1996-08-13 Hercules Incorporated Polyolefin fiber
US5286843A (en) 1992-05-22 1994-02-15 Rohm And Haas Company Process for improving water-whitening resistance of pressure sensitive adhesives
US5292075A (en) 1992-05-29 1994-03-08 Knobbe, Martens, Olson & Bear Disposable diaper recycling process
JP3116291B2 (en) 1992-06-11 2000-12-11 日本板硝子株式会社 Treatment liquid for glass fiber for rubber reinforcement and glass fiber cord for rubber reinforcement
JP2625350B2 (en) 1992-06-26 1997-07-02 株式会社コーロン Composite fiber
US5290654A (en) 1992-07-29 1994-03-01 Xerox Corporation Microsuspension processes for toner compositions
US5382400A (en) 1992-08-21 1995-01-17 Kimberly-Clark Corporation Nonwoven multicomponent polymeric fabric and method for making same
US5336552A (en) 1992-08-26 1994-08-09 Kimberly-Clark Corporation Nonwoven fabric made with multicomponent polymeric strands including a blend of polyolefin and ethylene alkyl acrylate copolymer
US5389068A (en) 1992-09-01 1995-02-14 Kimberly-Clark Corporation Tampon applicator
CA2092604A1 (en) 1992-11-12 1994-05-13 Richard Swee-Chye Yeo Hydrophilic, multicomponent polymeric strands and nonwoven fabrics made therewith
JP2818693B2 (en) 1992-11-18 1998-10-30 ヘキスト・セラニーズ・コーポレーション Fibrous structure containing immobilized particulate matter and method for producing the same
US5482772A (en) 1992-12-28 1996-01-09 Kimberly-Clark Corporation Polymeric strands including a propylene polymer composition and nonwoven fabric and articles made therewith
US5372985A (en) 1993-02-09 1994-12-13 Minnesota Mining And Manufacturing Company Thermal transfer systems having delaminating coatings
JP2679930B2 (en) 1993-02-10 1997-11-19 昇 丸山 Hot water supply device
US5292855A (en) 1993-02-18 1994-03-08 Eastman Kodak Company Water-dissipatable polyesters and amides containing near infrared fluorescent compounds copolymerized therein
US5274025A (en) 1993-02-19 1993-12-28 Eastman Kodak Company Ink and coating compositions containing a blend of water-dispersible polyester and hydantoin-formaldehyde resins
ES2218521T3 (en) * 1993-03-09 2004-11-16 Trevira Gmbh ELECTREPE FIBERS WITH AN IMPROVED LOAD STABILITY, THE PROCESS FOR THEIR PRODUCTION AND TEXTILE MATERIALS CONTAINING THESE ELECTREPE FIBERS.
US5386003A (en) 1993-03-15 1995-01-31 Eastman Chemical Company Oil absorbing polymers
US5374357A (en) 1993-03-19 1994-12-20 D. W. Walker & Associates Filter media treatment of a fluid flow to remove colloidal matter
US5369211A (en) 1993-04-01 1994-11-29 Eastman Chemical Company Water-dispersible sulfo-polyester compostions having a TG of greater than 89°C.
JP3317703B2 (en) 1993-04-08 2002-08-26 ユニチカ株式会社 Fiber having network structure and method for producing the same
DE69433344T2 (en) 1993-04-27 2004-04-15 The Dow Chemical Co., Midland Bicomponent fibers with at least one elastic component, fabric and articles made therefrom
US5369210A (en) 1993-07-23 1994-11-29 Eastman Chemical Company Heat-resistant water-dispersible sulfopolyester compositions
US5466518A (en) 1993-08-17 1995-11-14 Kimberly-Clark Corporation Binder compositions and web materials formed thereby
US5593778A (en) 1993-09-09 1997-01-14 Kanebo, Ltd. Biodegradable copolyester, molded article produced therefrom and process for producing the molded article
JP3131100B2 (en) 1993-10-20 2001-01-31 帝人株式会社 Polyester composition and its fiber
US5378757A (en) 1993-11-15 1995-01-03 Eastman Chemical Company Water-dissipatable alkyd resins and coatings prepared therefrom
US5914366A (en) 1993-11-24 1999-06-22 Cytec Technology Corp. Multimodal emulsions and processes for preparing multimodal emulsions
KR970700743A (en) 1993-12-29 1997-02-12 해리 제이. 그윈넬 WATER-DISPERSIBLE ADHESIVE COMPOSITION AND PROCESS
US5423432A (en) 1993-12-30 1995-06-13 Eastman Chemical Company Water-dissipatable polyesters and amides containing near infrared fluorescent compounds copolymerized therein
CA2141768A1 (en) 1994-02-07 1995-08-08 Tatsuro Mizuki High-strength ultra-fine fiber construction, method for producing the same and high-strength conjugate fiber
FR2720400B1 (en) 1994-05-30 1996-06-28 Rhone Poulenc Chimie New sulfonated polyesters and their use as an anti-fouling agent in detergent, rinsing, softening and textile treatment compositions.
US5607491A (en) 1994-05-04 1997-03-04 Jackson; Fred L. Air filtration media
US5843311A (en) 1994-06-14 1998-12-01 Dionex Corporation Accelerated solvent extraction method
US5575918A (en) 1995-02-28 1996-11-19 Henkel Corporation Method for recovery of polymers
US5498468A (en) 1994-09-23 1996-03-12 Kimberly-Clark Corporation Fabrics composed of ribbon-like fibrous material and method to make the same
US6162890A (en) 1994-10-24 2000-12-19 Eastman Chemical Company Water-dispersible block copolyesters useful as low-odor adhesive raw materials
DE69532875T2 (en) 1994-10-24 2004-08-19 Eastman Chemical Co., Kingsport Water-dispersible block copolyesters
DE69528076T2 (en) 1994-10-31 2003-04-30 Kimberly Clark Co HIGH DENSITY FIBERGLASS FILTER MEDIA
US5753351A (en) 1994-11-18 1998-05-19 Teijin Limited Nubuck-like woven fabric and method of producing same
FR2728182B1 (en) 1994-12-16 1997-01-24 Coatex Sa PROCESS FOR OBTAINING GRINDING AND / OR DISPERSING AGENTS BY PHYSICOCHEMICAL SEPARATION, AGENTS OBTAINED AND USES THEREOF
WO1996019599A1 (en) 1994-12-22 1996-06-27 Biotec Biologische Naturverpackungen Gmbh Technical and non-technical textile products and packaging materials
US5888916A (en) 1994-12-28 1999-03-30 Asahi Kasei Kogyo Kabushiki Kaisha Wet-laid nonwoven fabric for battery separator, its production method and sealed type secondary battery
US6579814B1 (en) * 1994-12-30 2003-06-17 3M Innovative Properties Company Dispersible compositions and articles of sheath-core microfibers and method of disposal for such compositions and articles
US5472518A (en) * 1994-12-30 1995-12-05 Minnesota Mining And Manufacturing Company Method of disposal for dispersible compositions and articles
US5779736A (en) 1995-01-19 1998-07-14 Eastman Chemical Company Process for making fibrillated cellulose acetate staple fibers
US5635071A (en) 1995-01-20 1997-06-03 Zenon Airport Enviromental, Inc. Recovery of carboxylic acids from chemical plant effluents
TW317577B (en) 1995-01-25 1997-10-11 Toray Industries
US20060064069A1 (en) 2000-04-12 2006-03-23 Rajala Gregory J Disposable undergarment and related manufacturing equipment and processes
US5472600A (en) 1995-02-01 1995-12-05 Minnesota Mining And Manufacturing Company Gradient density filter
JP4180653B2 (en) 1995-02-17 2008-11-12 三菱製紙株式会社 Alkaline battery separator nonwoven fabric
TW293049B (en) 1995-03-08 1996-12-11 Unitika Ltd
US5559205A (en) 1995-05-18 1996-09-24 E. I. Du Pont De Nemours And Company Sulfonate-containing polyesters dyeable with basic dyes
US5759926A (en) 1995-06-07 1998-06-02 Kimberly-Clark Worldwide, Inc. Fine denier fibers and fabrics made therefrom
JP2001519856A (en) 1995-06-07 2001-10-23 キンバリー クラーク ワールドワイド インコーポレイテッド Fine denier fiber and fabric made from the fiber
US6352948B1 (en) 1995-06-07 2002-03-05 Kimberly-Clark Worldwide, Inc. Fine fiber composite web laminates
US5620785A (en) 1995-06-07 1997-04-15 Fiberweb North America, Inc. Meltblown barrier webs and processes of making same
US6229002B1 (en) 1995-06-07 2001-05-08 Nexstar Pharmaceuticlas, Inc. Platelet derived growth factor (PDGF) nucleic acid ligand complexes
US5496627A (en) 1995-06-16 1996-03-05 Eastman Chemical Company Composite fibrous filters
US5948710A (en) 1995-06-30 1999-09-07 Kimberly-Clark Worldwide, Inc. Water-dispersible fibrous nonwoven coform composites
UA28104C2 (en) * 1995-06-30 2000-10-16 Кімберлі-Кларк Уорлдвайд Інк. Multi-component fiber, non-woven material and articles made of that material
US5952251A (en) 1995-06-30 1999-09-14 Kimberly-Clark Corporation Coformed dispersible nonwoven fabric bonded with a hybrid system
JP3475596B2 (en) 1995-08-01 2003-12-08 チッソ株式会社 Durable hydrophilic fibers, cloths and moldings
US5652048A (en) 1995-08-02 1997-07-29 Kimberly-Clark Worldwide, Inc. High bulk nonwoven sorbent
BR9610447B1 (en) 1995-08-02 2010-08-10 METHOD FOR FORMING ARTIFICIAL FIBERS OF A LIQUID RESIN.
US5646237A (en) 1995-08-15 1997-07-08 Eastman Chemical Company Water-dispersible copolyester-ether compositions
EP0847263B2 (en) 1995-08-28 2011-03-09 Kimberly-Clark Worldwide, Inc. Thermoplastic fibrous nonwoven webs for use as core wraps in absorbent articles
US5744538A (en) 1995-08-28 1998-04-28 Eastman Chemical Company Water dispersible adhesive compositions
US5750605A (en) 1995-08-31 1998-05-12 National Starch And Chemical Investment Holding Corporation Hot melt adhesives based on sulfonated polyesters
US5798078A (en) 1996-07-11 1998-08-25 Kimberly-Clark Worldwide, Inc. Sulfonated polymers and method of sulfonating polymers
US6384108B1 (en) 1995-09-29 2002-05-07 Xerox Corporation Waterfast ink jet inks containing an emulsifiable polymer resin
DE19541326A1 (en) 1995-11-06 1997-05-07 Basf Ag Water-soluble or water-dispersible polyurethanes having terminal acid groups, their preparation and their use
KR100445769B1 (en) 1995-11-30 2004-10-15 킴벌리-클라크 월드와이드, 인크. Superfine Microfiber Nonwoven Web
US5672415A (en) 1995-11-30 1997-09-30 Kimberly-Clark Worldwide, Inc. Low density microfiber nonwoven fabric
US5728295A (en) 1996-04-19 1998-03-17 Fuji Hunt Photographic Chemicals, Inc. Apparatus for removing metal ions and/or complexes containing metal ions from a solution
US6730387B2 (en) 1996-04-24 2004-05-04 The Procter & Gamble Company Absorbent materials having improved structural stability in dry and wet states and making methods therefor
US5593807A (en) 1996-05-10 1997-01-14 Xerox Corporation Toner processes using sodium sulfonated polyester resins
WO1997043472A1 (en) 1996-05-14 1997-11-20 Shimadzu Corporation Spontaneously degradable fibers and goods made by using the same
US5658704A (en) 1996-06-17 1997-08-19 Xerox Corporation Toner processes
US5660965A (en) 1996-06-17 1997-08-26 Xerox Corporation Toner processes
US5895710A (en) 1996-07-10 1999-04-20 Kimberly-Clark Worldwide, Inc. Process for producing fine fibers and fabrics thereof
US5783503A (en) 1996-07-22 1998-07-21 Fiberweb North America, Inc. Meltspun multicomponent thermoplastic continuous filaments, products made therefrom, and methods therefor
JP3488784B2 (en) 1996-07-30 2004-01-19 ジーイー東芝シリコーン株式会社 Film-forming emulsion type silicone composition for airbag and airbag
US6235392B1 (en) 1996-08-23 2001-05-22 Weyerhaeuser Company Lyocell fibers and process for their preparation
US5916935A (en) 1996-08-27 1999-06-29 Henkel Corporation Polymeric thickeners for aqueous compositions
US6162537A (en) 1996-11-12 2000-12-19 Solutia Inc. Implantable fibers and medical articles
US6200669B1 (en) 1996-11-26 2001-03-13 Kimberly-Clark Worldwide, Inc. Entangled nonwoven fabrics and methods for forming the same
US5820982A (en) 1996-12-03 1998-10-13 Seydel Companies, Inc. Sulfoaryl modified water-soluble or water-dispersible resins from polyethylene terephthalate or terephthalates
US6168719B1 (en) 1996-12-27 2001-01-02 Kao Corporation Method for the purification of ionic polymers
US5952088A (en) * 1996-12-31 1999-09-14 Kimberly-Clark Worldwide, Inc. Multicomponent fiber
EP0954626B1 (en) 1996-12-31 2002-07-24 The Quantum Group, Inc. Composite elastomeric yarns
US5817740A (en) 1997-02-12 1998-10-06 E. I. Du Pont De Nemours And Company Low pill polyester
US6037055A (en) 1997-02-12 2000-03-14 E. I. Du Pont De Nemours And Company Low pill copolyester
US5935884A (en) 1997-02-14 1999-08-10 Bba Nonwovens Simpsonville, Inc. Wet-laid nonwoven nylon battery separator material
AU6262898A (en) 1997-02-14 1998-09-08 Cytec Technology Corp. Papermaking methods and compositions
US5837658A (en) 1997-03-26 1998-11-17 Stork; David J. Metal forming lubricant with differential solid lubricants
JP3588967B2 (en) 1997-04-03 2004-11-17 チッソ株式会社 Splittable composite fiber
US6183648B1 (en) 1997-04-04 2001-02-06 Geo Specialty Chemicals, Inc. Process for purification of organic sulfonates and novel product
DE69820206T2 (en) 1997-04-11 2004-11-04 Nissan Motor Co., Ltd., Yokohama Optical interference fiber and its use
US5785725A (en) 1997-04-14 1998-07-28 Johns Manville International, Inc. Polymeric fiber and glass fiber composite filter media
FR2763482B1 (en) 1997-05-26 1999-08-06 Picardie Lainiere THERMAL ADHESIVE COVERING WITH LARGE TITRATION FILAMENTS
US5970583A (en) 1997-06-17 1999-10-26 Firma Carl Freudenberg Nonwoven lap formed of very fine continuous filaments
US6294645B1 (en) 1997-07-25 2001-09-25 Hercules Incorporated Dry-strength system
US5976694A (en) 1997-10-03 1999-11-02 Kimberly-Clark Worldwide, Inc. Water-sensitive compositions for improved processability
US5993834A (en) 1997-10-27 1999-11-30 E-L Management Corp. Method for manufacture of pigment-containing cosmetic compositions
US6551353B1 (en) 1997-10-28 2003-04-22 Hills, Inc. Synthetic fibers for medical use and method of making the same
AU1802499A (en) 1997-12-03 1999-06-16 Ason Engineering, Inc. Nonwoven fabrics formed from ribbon-shaped fibers and method and apparatus for making the same
US6171440B1 (en) 1997-12-31 2001-01-09 Hercules Incorporated Process for repulping wet strength paper having cationic thermosetting resin
US5916725A (en) 1998-01-13 1999-06-29 Xerox Corporation Surfactant free toner processes
US5853944A (en) 1998-01-13 1998-12-29 Xerox Corporation Toner processes
JPH11217757A (en) 1998-01-30 1999-08-10 Unitika Ltd Staple fiber nonwoven fabric and its production
GB9803812D0 (en) 1998-02-25 1998-04-22 Albright & Wilson Uk Ltd Membrane filtration of polymer containing solutions
US6726841B2 (en) 1998-03-03 2004-04-27 A.B. Technologies Holding, L.L.C. Method for the purification and recovery of non-gelatin colloidal waste encapsulation materials
AU3091399A (en) 1998-03-17 1999-10-11 Ameritherm, Inc. Rf active compositions for use in adhesion, bonding and coating
US6348679B1 (en) 1998-03-17 2002-02-19 Ameritherm, Inc. RF active compositions for use in adhesion, bonding and coating
US6432850B1 (en) 1998-03-31 2002-08-13 Seiren Co., Ltd. Fabrics and rust proof clothes excellent in conductivity and antistatic property
US6702801B2 (en) 1998-05-07 2004-03-09 Kimberly-Clark Worldwide, Inc. Absorbent garment with an extensible backsheet
US6225243B1 (en) 1998-08-03 2001-05-01 Bba Nonwovens Simpsonville, Inc. Elastic nonwoven fabric prepared from bi-component filaments
US6550622B2 (en) 1998-08-27 2003-04-22 Koslow Technologies Corporation Composite filter medium and fluid filters containing same
USH2086H1 (en) 1998-08-31 2003-10-07 Kimberly-Clark Worldwide Fine particle liquid filtration media
JP3263370B2 (en) * 1998-09-25 2002-03-04 カネボウ株式会社 Alkaline water easily-eluting copolyester and method for producing the same
US6667424B1 (en) 1998-10-02 2003-12-23 Kimberly-Clark Worldwide, Inc. Absorbent articles with nits and free-flowing particles
US6838402B2 (en) 1999-09-21 2005-01-04 Fiber Innovation Technology, Inc. Splittable multicomponent elastomeric fibers
AU6509399A (en) 1998-10-06 2000-04-26 Fiber Innovation Technology, Inc. Splittable multicomponent elastomeric fibers
US6706189B2 (en) 1998-10-09 2004-03-16 Zenon Environmental Inc. Cyclic aeration system for submerged membrane modules
US6110636A (en) 1998-10-29 2000-08-29 Xerox Corporation Polyelectrolyte toner processes
WO2000030742A1 (en) 1998-11-23 2000-06-02 Zenon Environmental Inc. Water filtration using immersed membranes
ES2216425T3 (en) 1998-12-16 2004-10-16 Kuraray Co., Ltd. THERMOPLASTIC FIBERS OF POLYVINYL ALCOHOL AND ITS PREPARATION PROCEDURE.
US6369136B2 (en) 1998-12-31 2002-04-09 Eastman Kodak Company Electrophotographic toner binders containing polyester ionomers
US6110588A (en) 1999-02-05 2000-08-29 3M Innovative Properties Company Microfibers and method of making
US6630231B2 (en) 1999-02-05 2003-10-07 3M Innovative Properties Company Composite articles reinforced with highly oriented microfibers
FR2790489B1 (en) 1999-03-01 2001-04-20 Freudenberg Carl Fa TABLECLOTH NOT WOVEN IN THERMOLIA FILAMENTS OR FIBERS
JP3704249B2 (en) 1999-03-05 2005-10-12 帝人ファイバー株式会社 Hydrophilic fiber
ATE302836T1 (en) 1999-03-09 2005-09-15 Rhodia Chimie Sa SULFONATED COPOLYMER AND METHOD FOR CLEANING SURFACES AND/OR PRODUCING STAIN-RESISTANT PROPERTIES OF SUCH SURFACES AND/OR FOR REMOVAL OF STAINS OR DIAMING
US6020420A (en) 1999-03-10 2000-02-01 Eastman Chemical Company Water-dispersible polyesters
JP3474482B2 (en) 1999-03-15 2003-12-08 高砂香料工業株式会社 Biodegradable composite fiber and method for producing the same
US6110249A (en) 1999-03-26 2000-08-29 Bha Technologies, Inc. Filter element with membrane and bicomponent substrate
US6509092B1 (en) 1999-04-05 2003-01-21 Fiber Innovation Technology Heat bondable biodegradable fibers with enhanced adhesion
US6441267B1 (en) 1999-04-05 2002-08-27 Fiber Innovation Technology Heat bondable biodegradable fiber
US7091140B1 (en) 1999-04-07 2006-08-15 Polymer Group, Inc. Hydroentanglement of continuous polymer filaments
DE19917275B4 (en) 1999-04-16 2004-02-26 Carl Freudenberg Kg cleaning cloth
KR100750281B1 (en) 1999-05-20 2007-08-20 다우 글로벌 테크놀로지스 인크. A continuous process of extruding and mechanically dispersing a polymeric resin in an aqueous or non-aqueous medium
US6762339B1 (en) 1999-05-21 2004-07-13 3M Innovative Properties Company Hydrophilic polypropylene fibers having antimicrobial activity
US6533938B1 (en) 1999-05-27 2003-03-18 Worcester Polytechnic Institue Polymer enhanced diafiltration: filtration using PGA
US6723428B1 (en) 1999-05-27 2004-04-20 Foss Manufacturing Co., Inc. Anti-microbial fiber and fibrous products
US6120889A (en) 1999-06-03 2000-09-19 Eastman Chemical Company Low melt viscosity amorphous copolyesters with enhanced glass transition temperatures
AU3935700A (en) 1999-06-21 2001-01-04 Rohm And Haas Company Ultrafiltration processes for the recovery of polymeric latices from whitewater
US6177607B1 (en) 1999-06-25 2001-01-23 Kimberly-Clark Worldwide, Inc. Absorbent product with nonwoven dampness inhibitor
GB9915039D0 (en) 1999-06-28 1999-08-25 Eastman Chem Co Aqueous application of additives to polymeric particles
DE19934442C2 (en) 1999-07-26 2001-09-20 Freudenberg Carl Fa Process for producing a nonwoven and nonwoven for producing cleanroom protective clothing
US20010052494A1 (en) 1999-10-25 2001-12-20 Pierre Cote Chemical cleaning backwash for normally immersed membranes
US6649888B2 (en) 1999-09-23 2003-11-18 Codaco, Inc. Radio frequency (RF) heating system
JP3404555B2 (en) 1999-09-24 2003-05-12 チッソ株式会社 Hydrophilic fibers and nonwoven fabrics, processed nonwoven fabrics using them
US6589426B1 (en) 1999-09-29 2003-07-08 Zenon Environmental Inc. Ultrafiltration and microfiltration module and system
JP2001123335A (en) 1999-10-21 2001-05-08 Nippon Ester Co Ltd Split-type polyester conjugated fiber
EP1276548B1 (en) 1999-10-29 2008-12-17 HOLLINGSWORTH &amp; VOSE COMPANY Filter media
US6177193B1 (en) 1999-11-30 2001-01-23 Kimberly-Clark Worldwide, Inc. Biodegradable hydrophilic binder fibers
DE60030162T2 (en) 1999-12-01 2007-08-09 Rhodia Inc. PROCESS FOR PREPARING SULFONATED POLYESTERS
US6576716B1 (en) 1999-12-01 2003-06-10 Rhodia, Inc Process for making sulfonated polyester compounds
JP5770962B2 (en) 1999-12-07 2015-08-26 ウィリアム・マーシュ・ライス・ユニバーシティ Oriented nanofibers embedded in a polymer matrix
US6583075B1 (en) 1999-12-08 2003-06-24 Fiber Innovation Technology, Inc. Dissociable multicomponent fibers containing a polyacrylonitrile polymer component
EP1259562B1 (en) 1999-12-22 2006-02-15 Nektar Therapeutics Al, Corporation Sterically hindered derivatives of water soluble polymers
JP3658303B2 (en) 2000-09-01 2005-06-08 ユニ・チャーム株式会社 Elastic stretch composite sheet and method for producing the same
CN100453714C (en) 2000-01-20 2009-01-21 因维斯塔技术有限公司 Method for high-speed spinning of bicomponent fibers
DE10002778B4 (en) 2000-01-22 2012-05-24 Robert Groten Use of a microfilament nonwoven fabric as a cleaning cloth
US6332994B1 (en) 2000-02-14 2001-12-25 Basf Corporation High speed spinning of sheath/core bicomponent fibers
DE10013315C2 (en) 2000-03-17 2002-06-06 Freudenberg Carl Kg Pleated filter from a multi-layer filter medium
US6429261B1 (en) 2000-05-04 2002-08-06 Kimberly-Clark Worldwide, Inc. Ion-sensitive, water-dispersible polymers, a method of making same and items using same
US6316592B1 (en) 2000-05-04 2001-11-13 General Electric Company Method for isolating polymer resin from solution slurries
CA2409364A1 (en) 2000-05-26 2001-11-29 Ciba Specialty Chemicals Holding Inc. Process for preparing solutions of anionic organic compounds
US6620503B2 (en) 2000-07-26 2003-09-16 Kimberly-Clark Worldwide, Inc. Synthetic fiber nonwoven web and method
US7365118B2 (en) 2003-07-08 2008-04-29 Los Alamos National Security, Llc Polymer-assisted deposition of films
US6776858B2 (en) 2000-08-04 2004-08-17 E.I. Du Pont De Nemours And Company Process and apparatus for making multicomponent meltblown web fibers and webs
US6899810B1 (en) 2000-08-11 2005-05-31 Millipore Corporation Fluid filtering device
US6743273B2 (en) 2000-09-05 2004-06-01 Donaldson Company, Inc. Polymer, polymer microfiber, polymer nanofiber and applications including filter structures
US20020031967A1 (en) 2000-09-08 2002-03-14 Japan Vilene Co., Ltd. Fine-fibers-dispersed nonwoven fabric, process and apparatus for manufacturing same, and sheet material containing same
MXPA03002597A (en) 2000-09-21 2005-02-25 Outlast Technologies Inc Multi-component fibers having reversible thermal properties.
US6855422B2 (en) 2000-09-21 2005-02-15 Monte C. Magill Multi-component fibers having enhanced reversible thermal properties and methods of manufacturing thereof
US20050208286A1 (en) 2000-09-21 2005-09-22 Hartmann Mark H Polymeric composites having enhanced reversible thermal properties and methods of forming thereof
US7160612B2 (en) 2000-09-21 2007-01-09 Outlast Technologies, Inc. Multi-component fibers having enhanced reversible thermal properties and methods of manufacturing thereof
EP1715088B1 (en) 2000-09-21 2008-09-03 Outlast Technologies, Inc. Multi-component fibers having reversible thermal properties
US6361784B1 (en) 2000-09-29 2002-03-26 The Procter & Gamble Company Soft, flexible disposable wipe with embossing
JP2004514797A (en) 2000-09-29 2004-05-20 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Stretchable polymer fiber, spinneret useful for molding the fiber, and products manufactured from the fiber
CN1303274C (en) 2000-10-04 2007-03-07 纳幕尔杜邦公司 Meltblown web
US20020127939A1 (en) 2000-11-06 2002-09-12 Hwo Charles Chiu-Hsiung Poly (trimethylene terephthalate) based meltblown nonwovens
KR20010044145A (en) 2000-11-27 2001-06-05 구광시 A sea-island typed composite fiber for warp knit terated raising
US6331606B1 (en) 2000-12-01 2001-12-18 E. I. Du Pont De Nemours And Comapny Polyester composition and process therefor
US6485828B2 (en) 2000-12-01 2002-11-26 Oji Paper Co., Ltd. Flat synthetic fiber, method for preparing the same and non-woven fabric prepared using the same
US6664437B2 (en) 2000-12-21 2003-12-16 Kimberly-Clark Worldwide, Inc. Layered composites for personal care products
US6420024B1 (en) 2000-12-21 2002-07-16 3M Innovative Properties Company Charged microfibers, microfibrillated articles and use thereof
ES2378982T3 (en) 2000-12-28 2012-04-19 Danisco A/S Separation procedure
US6838403B2 (en) 2000-12-28 2005-01-04 Kimberly-Clark Worldwide, Inc. Breathable, biodegradable/compostable laminates
US6946413B2 (en) 2000-12-29 2005-09-20 Kimberly-Clark Worldwide, Inc. Composite material with cloth-like feel
ES2204218B1 (en) 2001-01-17 2005-06-01 Mopatex, S.A. MOP FOR MOPS.
US6586529B2 (en) 2001-02-01 2003-07-01 Kimberly-Clark Worldwide, Inc. Water-dispersible polymers, a method of making same and items using same
CN1328300C (en) 2001-02-23 2007-07-25 东洋纺织株式会社 Polyester catalyst for polymerization, polyester and method thereby
US6506853B2 (en) 2001-02-28 2003-01-14 E. I. Du Pont De Nemours And Company Copolymer comprising isophthalic acid
EP1243675A1 (en) 2001-03-23 2002-09-25 Nan Ya Plastics Corp. Microfiber and its manufacturing method
US6381817B1 (en) 2001-03-23 2002-05-07 Polymer Group, Inc. Composite nonwoven fabric
WO2002088438A1 (en) 2001-04-26 2002-11-07 Kolon Industries, Inc A sea-island typed conjugate multi filament comprising dope dyeing component, and a process of preparing for the same
US20020168912A1 (en) 2001-05-10 2002-11-14 Bond Eric Bryan Multicomponent fibers comprising starch and biodegradable polymers
US20030077444A1 (en) 2001-05-10 2003-04-24 The Procter & Gamble Company Multicomponent fibers comprising starch and polymers
US6743506B2 (en) 2001-05-10 2004-06-01 The Procter & Gamble Company High elongation splittable multicomponent fibers comprising starch and polymers
US6946506B2 (en) 2001-05-10 2005-09-20 The Procter & Gamble Company Fibers comprising starch and biodegradable polymers
US7195814B2 (en) 2001-05-15 2007-03-27 3M Innovative Properties Company Microfiber-entangled products and related methods
US6645618B2 (en) 2001-06-15 2003-11-11 3M Innovative Properties Company Aliphatic polyester microfibers, microfibrillated articles and use thereof
DE10129458A1 (en) 2001-06-19 2003-01-02 Celanese Ventures Gmbh Improved polymer films based on polyazoles
JP4212787B2 (en) 2001-07-02 2009-01-21 株式会社クラレ Leather-like sheet
CA2454176A1 (en) 2001-07-17 2003-01-30 Dow Global Technologies Inc. Elastic, heat and moisture resistant bicomponent and biconstituent fibers
US20040081829A1 (en) 2001-07-26 2004-04-29 John Klier Sulfonated substantiallly random interpolymer-based absorbent materials
US6657017B2 (en) 2001-07-27 2003-12-02 Rhodia Inc Sulfonated polyester compounds with enhanced shelf stability and processes of making the same
KR100517044B1 (en) 2001-07-31 2005-09-26 가부시키가이샤 구라레 Leather-like sheet and method for production thereof
US6746779B2 (en) 2001-08-10 2004-06-08 E. I. Du Pont De Nemours And Company Sulfonated aliphatic-aromatic copolyesters
MXPA04002297A (en) 2001-09-24 2004-06-29 Procter & Gamble A soft absorbent web material.
US6998068B2 (en) 2003-08-15 2006-02-14 3M Innovative Properties Company Acene-thiophene semiconductors
US7309498B2 (en) 2001-10-10 2007-12-18 Belenkaya Bronislava G Biodegradable absorbents and methods of preparation
US6906160B2 (en) 2001-11-06 2005-06-14 Dow Global Technologies Inc. Isotactic propylene copolymer fibers, their preparation and use
US20060204753A1 (en) 2001-11-21 2006-09-14 Glen Simmonds Stretch Break Method and Product
GB0129728D0 (en) 2001-12-12 2002-01-30 Dupont Teijin Films Us Ltd Plymeric film
US6787081B2 (en) 2001-12-14 2004-09-07 Nan Ya Plastics Corporation Manufacturing method for differential denier and differential cross section fiber and fabric
US6780942B2 (en) 2001-12-20 2004-08-24 Eastman Kodak Company Method of preparation of porous polyester particles
US6902796B2 (en) 2001-12-28 2005-06-07 Kimberly-Clark Worldwide, Inc. Elastic strand bonded laminate
US7285209B2 (en) 2001-12-28 2007-10-23 Guanghua Yu Method and apparatus for separating emulsified water from hydrocarbons
US6541175B1 (en) 2002-02-04 2003-04-01 Xerox Corporation Toner processes
SG128436A1 (en) 2002-02-08 2007-01-30 Kuraray Co Nonwoven fabric for wiper
SE0200476D0 (en) 2002-02-15 2002-02-15 Sca Hygiene Prod Ab Hydroentangled microfibre material and process for its preparation
US20030166371A1 (en) 2002-02-15 2003-09-04 Sca Hygiene Products Ab Hydroentangled microfibre material and method for its manufacture
US6638677B2 (en) 2002-03-01 2003-10-28 Xerox Corporation Toner processes
JP3826052B2 (en) 2002-03-04 2006-09-27 株式会社クラレ Ultrafine fiber bundle and method for producing the same
US6669814B2 (en) 2002-03-08 2003-12-30 Rock-Tenn Company Multi-ply paperboard prepared from recycled materials and methods of manufacturing same
KR101130879B1 (en) 2002-04-04 2012-03-28 더 유니버시티 오브 아크론 Non-woven fiber assemblies
US7135135B2 (en) 2002-04-11 2006-11-14 H.B. Fuller Licensing & Financing, Inc. Superabsorbent water sensitive multilayer construction
US7186344B2 (en) 2002-04-17 2007-03-06 Water Visions International, Inc. Membrane based fluid treatment systems
JP4163894B2 (en) 2002-04-24 2008-10-08 帝人株式会社 Separator for lithium ion secondary battery
US6890649B2 (en) 2002-04-26 2005-05-10 3M Innovative Properties Company Aliphatic polyester microfibers, microfibrillated articles and use thereof
DE60327314D1 (en) 2002-05-02 2009-06-04 Teijin Techno Products Ltd LADIES OF HEAT-RESISTANT SYNTHESIS FIBER
US7388058B2 (en) 2002-05-13 2008-06-17 E.I. Du Pont De Nemours And Company Polyester blend compositions and biodegradable films produced therefrom
US6861142B1 (en) 2002-06-06 2005-03-01 Hills, Inc. Controlling the dissolution of dissolvable polymer components in plural component fibers
US7011653B2 (en) 2002-06-07 2006-03-14 Kimberly-Clark Worldwide, Inc. Absorbent pant garments having high leg cuts
JP4027728B2 (en) 2002-06-21 2007-12-26 帝人ファイバー株式会社 Nonwoven fabric made of polyester staple fibers
WO2004001375A2 (en) 2002-06-21 2003-12-31 Burntside Partners Inc Multi-functional product markers and methods for making and using the same
EP1382730A1 (en) 2002-07-15 2004-01-21 Paul Hartmann AG Cosmetic cotton pad
US6764802B2 (en) 2002-07-29 2004-07-20 Xerox Corporation Chemical aggregation process using inline mixer
US6893711B2 (en) 2002-08-05 2005-05-17 Kimberly-Clark Worldwide, Inc. Acoustical insulation material containing fine thermoplastic fibers
US20050026527A1 (en) 2002-08-05 2005-02-03 Schmidt Richard John Nonwoven containing acoustical insulation laminate
KR101029515B1 (en) 2002-08-05 2011-04-18 도레이 카부시키가이샤 Porous fiber
JP4272393B2 (en) 2002-08-07 2009-06-03 互応化学工業株式会社 Method for producing aqueous flame-retardant polyester resin
CN1293260C (en) 2002-08-07 2007-01-03 东丽株式会社 Artificial suede-type leather and process for producing the same
JP4208517B2 (en) 2002-08-07 2009-01-14 富士フイルム株式会社 Polymer solution concentration method and apparatus
US7405171B2 (en) 2002-08-08 2008-07-29 Chisso Corporation Elastic nonwoven fabric and fiber products manufactured therefrom
CN100336244C (en) 2002-08-22 2007-09-05 帝人株式会社 Non-aqueous secondary battery and separator used therefor
KR100681213B1 (en) 2002-09-11 2007-02-09 다나베 세이야꾸 가부시키가이샤 Process for the production of microspheres and unit therefor
US7951452B2 (en) 2002-09-30 2011-05-31 Kuraray Co., Ltd. Suede artificial leather and production method thereof
US6979380B2 (en) 2002-10-01 2005-12-27 Kimberly-Clark Worldwide, Inc. Three-piece disposable undergarment and method for the manufacture thereof
EP1405949B1 (en) 2002-10-02 2007-01-24 Fort James Corporation Paper products including surface treated thermally bondable fibers and methods of making the same
JP2004137319A (en) 2002-10-16 2004-05-13 Toray Ind Inc Copolyester composition and conjugate fiber obtained from the same
CN100588674C (en) 2002-10-18 2010-02-10 富士胶片株式会社 Method for filtering polymer solution, producing method of polymer solution, and method for preparing solvent
JP2004137418A (en) 2002-10-21 2004-05-13 Teijin Ltd Copolyester composition
JP4229115B2 (en) * 2002-10-23 2009-02-25 東レ株式会社 Nanofiber assembly
ATE536428T1 (en) 2002-10-23 2011-12-15 Toray Industries NANOFIBER AGGREGATE, PLASTIC ALLOY FIBER, HYBRID FIBER, FIBER STRUCTURES AND THEIR PRODUCTION PROCESS
ITMI20022291A1 (en) 2002-10-28 2004-04-29 Alcantara Spa THREE-DIMENSIONAL MICROFIBROUS FABRIC WITH SUEDE APPEARANCE AND ITS PREPARATION METHOD.
US6759124B2 (en) 2002-11-16 2004-07-06 Milliken & Company Thermoplastic monofilament fibers exhibiting low-shrink, high tenacity, and extremely high modulus levels
KR100667624B1 (en) 2002-11-26 2007-01-11 주식회사 코오롱 A high shrinkage side by side type composite filament, and a process of preparing the same
US8129450B2 (en) 2002-12-10 2012-03-06 Cellresin Technologies, Llc Articles having a polymer grafted cyclodextrin
US7022201B2 (en) 2002-12-23 2006-04-04 Kimberly-Clark Worldwide, Inc. Entangled fabric wipers for oil and grease absorbency
US6953622B2 (en) 2002-12-27 2005-10-11 Kimberly-Clark Worldwide, Inc. Biodegradable bicomponent fibers with improved thermal-dimensional stability
US6989194B2 (en) 2002-12-30 2006-01-24 E. I. Du Pont De Nemours And Company Flame retardant fabric
US20040127127A1 (en) 2002-12-30 2004-07-01 Dana Eagles Bicomponent monofilament
WO2004061180A1 (en) 2003-01-07 2004-07-22 Teijin Fibers Limited Polyester fiber structures
CA2513735C (en) 2003-01-08 2011-08-02 Teijin Fibers Limited Polyester-composite-staple-fiber nonwoven fabric
JP2004218125A (en) 2003-01-14 2004-08-05 Teijin Fibers Ltd Method for producing polyester fiber with modified cross section
AU2003292815A1 (en) 2003-01-16 2004-08-10 Teijin Fibers Limited Differential-shrinkage polyester combined filament yarn
US6780560B2 (en) 2003-01-29 2004-08-24 Xerox Corporation Toner processes
US7736737B2 (en) 2003-01-30 2010-06-15 Dow Global Technologies Inc. Fibers formed from immiscible polymer blends
US20040157037A1 (en) 2003-02-07 2004-08-12 Kuraray Co., Ltd. Suede-finished leather-like sheet and production method thereof
US7291389B1 (en) 2003-02-13 2007-11-06 Landec Corporation Article having temperature-dependent shape
DE602004028187D1 (en) 2003-03-10 2010-09-02 Kuraray Co Polyvinyl alcohol fibers and nonwoven fabrics containing them
US20050222956A1 (en) 2003-03-27 2005-10-06 Bristow Andrew N Method and system for providing goods or services to a subscriber of a communications network
JP4107133B2 (en) 2003-04-02 2008-06-25 株式会社ジェイテクト Torque sensor
US7163743B2 (en) 2003-04-04 2007-01-16 E. I. Du Pont De Nemours And Company Polyester monofilaments
JP3828877B2 (en) 2003-04-10 2006-10-04 大成化工株式会社 Method for producing a coloring agent (colorant) having excellent color development
US20040211729A1 (en) 2003-04-25 2004-10-28 Sunkara Hari Babu Processes for recovering oligomers of glycols and polymerization catalysts from waste streams
EP2267077A1 (en) 2003-05-02 2010-12-29 E. I. du Pont de Nemours and Company Polyesters containing microfibers, and methods for making and using same
US7297644B2 (en) 2003-05-28 2007-11-20 Air Products Polymers, L.P. Nonwoven binders with high wet/dry tensile strength ratio
US20040242838A1 (en) 2003-06-02 2004-12-02 Duan Jiwen F. Sulfonated polyester and process therewith
US7431869B2 (en) 2003-06-04 2008-10-07 Hills, Inc. Methods of forming ultra-fine fibers and non-woven webs
US6787245B1 (en) 2003-06-11 2004-09-07 E. I. Du Pont De Nemours And Company Sulfonated aliphatic-aromatic copolyesters and shaped articles produced therefrom
JP2005002510A (en) 2003-06-12 2005-01-06 Teijin Cordley Ltd Method for producing conjugate fiber
US20040260034A1 (en) 2003-06-19 2004-12-23 Haile William Alston Water-dispersible fibers and fibrous articles
US7687143B2 (en) 2003-06-19 2010-03-30 Eastman Chemical Company Water-dispersible and multicomponent fibers from sulfopolyesters
US8513147B2 (en) 2003-06-19 2013-08-20 Eastman Chemical Company Nonwovens produced from multicomponent fibers
JP2006528282A (en) * 2003-06-19 2006-12-14 イーストマン ケミカル カンパニー Water dispersible multicomponent fiber from sulfopolyester
US6974862B2 (en) 2003-06-20 2005-12-13 Kensey Nash Corporation High density fibrous polymers suitable for implant
JP4419549B2 (en) 2003-07-18 2010-02-24 東レ株式会社 Ultra-fine short fiber nonwoven fabric and leather-like sheet and production method thereof
US20050026526A1 (en) 2003-07-30 2005-02-03 Verdegan Barry M. High performance filter media with internal nanofiber structure and manufacturing methodology
US7220815B2 (en) 2003-07-31 2007-05-22 E.I. Du Pont De Nemours And Company Sulfonated aliphatic-aromatic copolyesters and shaped articles produced therefrom
DE10335451A1 (en) 2003-08-02 2005-03-10 Bayer Materialscience Ag Method for removing volatile compounds from mixtures by means of micro-evaporator
US7087301B2 (en) 2003-08-06 2006-08-08 Fina Technology, Inc. Bicomponent fibers of syndiotactic polypropylene
US7306735B2 (en) 2003-09-12 2007-12-11 General Electric Company Process for the removal of contaminants from water
US7329723B2 (en) 2003-09-18 2008-02-12 Eastman Chemical Company Thermal crystallization of polyester pellets in liquid
US7871946B2 (en) 2003-10-09 2011-01-18 Kuraray Co., Ltd. Nonwoven fabric composed of ultra-fine continuous fibers, and production process and application thereof
US7513004B2 (en) 2003-10-31 2009-04-07 Whirlpool Corporation Method for fluid recovery in a semi-aqueous wash process
US7432219B2 (en) 2003-10-31 2008-10-07 Sca Hygiene Products Ab Hydroentangled nonwoven material
US20050106982A1 (en) 2003-11-17 2005-05-19 3M Innovative Properties Company Nonwoven elastic fibrous webs and methods for making them
JP2005154450A (en) 2003-11-20 2005-06-16 Teijin Fibers Ltd Copolyester and splittable polyester conjugate fiber
US7179376B2 (en) 2003-11-24 2007-02-20 Ppg Industries Ohio, Inc. Method and system for removing residual water from excess washcoat by ultrafiltration
FR2862664B1 (en) 2003-11-25 2006-03-17 Chavanoz Ind COMPOSITE WIRE COMPRISING A CONTINUOUS WIRE AND A MATRIX COMPRISING A FOAM POLYMER
US6949288B2 (en) 2003-12-04 2005-09-27 Fiber Innovation Technology, Inc. Multicomponent fiber with polyarylene sulfide component
WO2005059215A2 (en) 2003-12-15 2005-06-30 North Carolina State University Improving physical and mechanical properties of fabrics by hydroentangling
US7194788B2 (en) 2003-12-23 2007-03-27 Kimberly-Clark Worldwide, Inc. Soft and bulky composite fabrics
DE602004020800D1 (en) 2003-12-26 2009-06-04 Kaneka Corp SHRINKABLE ACRYLIC FIBER AND METHOD FOR THE PRODUCTION THEREOF
US20050148261A1 (en) 2003-12-30 2005-07-07 Kimberly-Clark Worldwide, Inc. Nonwoven webs having reduced lint and slough
US7947864B2 (en) 2004-01-07 2011-05-24 Kimberly-Clark Worldwide, Inc. Low profile absorbent pantiliner
KR20050073909A (en) 2004-01-12 2005-07-18 주식회사 휴비스 Ultra fine conjugate ptt fibers for artificial leather and manufacturing method thereof
WO2005123599A2 (en) 2004-01-20 2005-12-29 Boundless Corporation Highly microporous polymers and methods for producing and using the same
US7452927B2 (en) 2004-01-30 2008-11-18 E. I. Du Pont De Nemours And Company Aliphatic-aromatic polyesters, and articles made therefrom
US20060194027A1 (en) 2004-02-04 2006-08-31 North Carolina State University Three-dimensional deep molded structures with enhanced properties
TWI321171B (en) 2004-02-23 2010-03-01 Teijin Fibers Ltd Synthetic staple fibers for an air-laid nonwoven fabric
US7897078B2 (en) 2004-03-09 2011-03-01 3M Innovative Properties Company Methods of manufacturing a stretched mechanical fastening web laminate
WO2005089913A1 (en) 2004-03-16 2005-09-29 Sri International Membrane purification system
US7101623B2 (en) 2004-03-19 2006-09-05 Dow Global Technologies Inc. Extensible and elastic conjugate fibers and webs having a nontacky feel
JP4473867B2 (en) 2004-03-30 2010-06-02 帝人ファイバー株式会社 Sea-island type composite fiber bundle and manufacturing method thereof
US20050227068A1 (en) 2004-03-30 2005-10-13 Innovation Technology, Inc. Taggant fibers
BRPI0509999A (en) 2004-04-19 2007-10-16 Procter & Gamble nanofiber articles for use as barriers
ATE485413T1 (en) 2004-04-19 2010-11-15 Procter & Gamble FIBERS, NON-WOVEN FABRICS AND PRODUCTS WITH NANOFIBERS MADE OF POLYMERS WITH A HIGH GLASS TRANSITION TEMPERATURE
US7195819B2 (en) 2004-04-23 2007-03-27 Invista North America S.A.R.L. Bicomponent fiber and yarn comprising same
US7285504B2 (en) 2004-04-23 2007-10-23 Air Products Polymers, L.P. Wet tensile strength of nonwoven webs
WO2005102683A1 (en) 2004-04-26 2005-11-03 Teijin Fibers Limited Conjugated-fiber structure and process for production thereof
DE102004026904A1 (en) 2004-06-01 2005-12-22 Basf Ag Highly functional, highly branched or hyperbranched polyesters and their preparation and use
JP2008504460A (en) 2004-06-24 2008-02-14 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Split fiber assembly
EP1766121B1 (en) 2004-06-29 2012-03-21 SCA Hygiene Products AB A hydroentangled split-fibre nonwoven material
US7772456B2 (en) 2004-06-30 2010-08-10 Kimberly-Clark Worldwide, Inc. Stretchable absorbent composite with low superaborbent shake-out
US7896940B2 (en) 2004-07-09 2011-03-01 3M Innovative Properties Company Self-supporting pleated filter media
US7358325B2 (en) 2004-07-09 2008-04-15 E. I. Du Pont De Nemours And Company Sulfonated aromatic copolyesters containing hydroxyalkanoic acid groups and shaped articles produced therefrom
US7193029B2 (en) 2004-07-09 2007-03-20 E. I. Du Pont De Nemours And Company Sulfonated copolyetherester compositions from hydroxyalkanoic acids and shaped articles produced therefrom
EP1781850A2 (en) 2004-07-16 2007-05-09 Reliance Industries Limited Self-crimping fully drawn high bulk yarns and method of producing thereof
MX2007000640A (en) 2004-07-16 2007-03-30 California Inst Of Techn Water treatment by dendrimer-enhanced filtration.
JP4713481B2 (en) 2004-07-16 2011-06-29 株式会社カネカ Acrylic shrinkable fiber and method for producing the same
US7238415B2 (en) 2004-07-23 2007-07-03 Catalytic Materials, Llc Multi-component conductive polymer structures and a method for producing same
JP2008507632A (en) 2004-07-23 2008-03-13 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド Wettable polyester fiber and fabric
DE102004036099B4 (en) 2004-07-24 2008-03-27 Carl Freudenberg Kg Multi-component spunbonded nonwoven, process for its preparation and use of multi-component spunbonded nonwovens
US7820568B2 (en) 2004-08-02 2010-10-26 Toray Industries, Inc. Leather-like sheet and production method thereof
US20060083917A1 (en) 2004-10-18 2006-04-20 Fiber Innovation Technology, Inc. Soluble microfilament-generating multicomponent fibers
WO2006043517A1 (en) 2004-10-19 2006-04-27 Toray Industries, Inc. Fabric for restraint device and process for producing the same
US7094466B2 (en) 2004-10-28 2006-08-22 E. I. Du Pont De Nemours And Company 3GT/4GT biocomponent fiber and preparation thereof
US7291270B2 (en) 2004-10-28 2007-11-06 Eastman Chemical Company Process for removal of impurities from an oxidizer purge stream
US7390760B1 (en) 2004-11-02 2008-06-24 Kimberly-Clark Worldwide, Inc. Composite nanofiber materials and methods for making same
CA2525315C (en) 2004-11-05 2010-02-23 Sara Lee Corporation Molded non-woven fabrics and methods of molding
US8021457B2 (en) 2004-11-05 2011-09-20 Donaldson Company, Inc. Filter media and structure
US8057567B2 (en) 2004-11-05 2011-11-15 Donaldson Company, Inc. Filter medium and breather filter structure
ES2541469T3 (en) 2004-11-05 2015-07-20 Donaldson Company, Inc. Spray separator
PL3138621T3 (en) 2004-11-05 2020-06-29 Donaldson Company, Inc. Filter medium and structure
KR101536669B1 (en) 2004-11-09 2015-07-15 더 보드 오브 리전츠 오브 더 유니버시티 오브 텍사스 시스템 The fabrication and application of nanofiber ribbons and sheets and twisted and non-twisted nanofiber yarns
US20060128247A1 (en) 2004-12-14 2006-06-15 Kimberly-Clark Worldwide, Inc. Embossed nonwoven fabric
US20060135020A1 (en) 2004-12-17 2006-06-22 Weinberg Mark G Flash spun web containing sub-micron filaments and process for forming same
US7238423B2 (en) 2004-12-20 2007-07-03 Kimberly-Clark Worldwide, Inc. Multicomponent fiber including elastic elements
US20060159918A1 (en) 2004-12-22 2006-07-20 Fiber Innovation Technology, Inc. Biodegradable fibers exhibiting storage-stable tenacity
US7465684B2 (en) 2005-01-06 2008-12-16 Buckeye Technologies Inc. High strength and high elongation wipe
DE102005001565A1 (en) 2005-01-13 2006-07-27 Bayer Materialscience Ag wood adhesives
US20080009574A1 (en) 2005-01-24 2008-01-10 Wellman, Inc. Polyamide-Polyester Polymer Blends and Methods of Making the Same
EP1689008B1 (en) 2005-01-26 2011-05-11 Japan Vilene Company, Ltd. Battery separator and battery comprising the same
JP5308031B2 (en) 2005-02-04 2013-10-09 ドナルドソン カンパニー,インコーポレイティド Ventilation filter and ventilation filtration assembly
US7214425B2 (en) 2005-02-10 2007-05-08 Supreme Elastic Corporation High performance fiber blend and products made therefrom
US7304125B2 (en) 2005-02-12 2007-12-04 Stratek Plastic Limited Process for the preparation of polymers from polymer slurries
US7717975B2 (en) 2005-02-16 2010-05-18 Donaldson Company, Inc. Reduced solidity web comprising fiber and fiber spacer or separation means
US8328782B2 (en) 2005-02-18 2012-12-11 The Procter & Gamble Company Hydrophobic surface coated light-weight nonwoven laminates for use in absorbent articles
JP4683959B2 (en) 2005-02-25 2011-05-18 花王株式会社 Nonwoven manufacturing method
JP2008534715A (en) 2005-03-25 2008-08-28 サイクリクス コーポレイション Preparation of low acid polybutylene terephthalate and preparation of macrocyclic polyester oligomers from low acid polybutylene terephthalate
US7358022B2 (en) 2005-03-31 2008-04-15 Xerox Corporation Control of particle growth with complexing agents
KR101492525B1 (en) 2005-04-01 2015-02-11 부케예 테크놀로지스 인코포레이티드 Nonwoven material for acoustic insulation, and process for manufacture
US7438777B2 (en) 2005-04-01 2008-10-21 North Carolina State University Lightweight high-tensile, high-tear strength bicomponent nonwoven fabrics
US7008694B1 (en) 2005-04-15 2006-03-07 Invista North America S.A.R.L. Polymer fibers, fabrics and equipment with a modified near infrared reflectance signature
US7959848B2 (en) 2005-05-03 2011-06-14 The University Of Akron Method and device for producing electrospun fibers
ATE448357T1 (en) 2005-05-10 2009-11-15 Voith Patent Gmbh PMC WITH SPLITABLE FIBERS
TWI297049B (en) 2005-05-17 2008-05-21 San Fang Chemical Industry Co Artificial leather having ultramicro fiber in conjugate fiber of substrate
US7897809B2 (en) 2005-05-19 2011-03-01 Eastman Chemical Company Process to produce an enrichment feed
US7914866B2 (en) 2005-05-26 2011-03-29 Kimberly-Clark Worldwide, Inc. Sleeved tissue product
JP4424263B2 (en) 2005-06-10 2010-03-03 株式会社豊田自動織機 Textile fabrics and composites
US7445834B2 (en) 2005-06-10 2008-11-04 Morin Brian G Polypropylene fiber for reinforcement of matrix materials
US7883772B2 (en) 2005-06-24 2011-02-08 North Carolina State University High strength, durable fabrics produced by fibrillating multilobal fibers
JP4664135B2 (en) 2005-07-08 2011-04-06 大京化学株式会社 Suede-like artificial leather with excellent flame retardancy and method for producing the same
TW200702505A (en) 2005-07-11 2007-01-16 Ind Tech Res Inst Nanofiber and fabrication methods thereof
EP1937393A4 (en) 2005-08-22 2010-04-07 Edmundo R Ashford Compact membrane unit and methods
US7695812B2 (en) 2005-09-16 2010-04-13 Dow Global Technologies, Inc. Fibers made from copolymers of ethylene/α-olefins
US7357985B2 (en) 2005-09-19 2008-04-15 E.I. Du Pont De Nemours And Company High crimp bicomponent fibers
US7875184B2 (en) 2005-09-22 2011-01-25 Eastman Chemical Company Crystallized pellet/liquid separator
JP4960616B2 (en) * 2005-09-29 2012-06-27 帝人ファイバー株式会社 Short fiber, method for producing the same, and precursor thereof
US20070074628A1 (en) 2005-09-30 2007-04-05 Jones David C Coalescing filtration medium and process
KR101298892B1 (en) 2005-09-30 2013-08-21 가부시키가이샤 구라레 Leather-like sheet and method of manufacturing the same
JP4648815B2 (en) 2005-10-12 2011-03-09 ナイルス株式会社 Material dryer
KR101367509B1 (en) 2005-10-19 2014-02-27 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Multilayer articles having acoustical absorbance properties and methods of making and using the same
US20070110980A1 (en) 2005-11-14 2007-05-17 Shah Ashok H Gypsum board liner providing improved combination of wet adhesion and strength
US20070110998A1 (en) 2005-11-15 2007-05-17 Steele Ronald E Polyamide yarn spinning process and modified yarn
US7497895B2 (en) 2005-11-18 2009-03-03 Exxonmobil Research And Engineering Company Membrane separation process
US20070122614A1 (en) 2005-11-30 2007-05-31 The Dow Chemical Company Surface modified bi-component polymeric fiber
DE602006009966D1 (en) 2005-12-06 2009-12-03 Invista Tech Sarl IN PROFILE SIX-CLASS FILAMENTS WITH THREE LARGER LAPPES AND THREE SMALLER LAPPES, TUFTING CARPET CARRIER WITH SUCH FILAMENTS AND CAPILLARY SPINNING NOZZLE FOR MANUFACTURING SUCH FILAMENTS
EP1970486B1 (en) 2005-12-14 2012-11-14 Kuraray Co., Ltd. Base for synthetic leather and synthetic leathers made by using the same
US7883604B2 (en) 2005-12-15 2011-02-08 Kimberly-Clark Worldwide, Inc. Creping process and products made therefrom
US20080039540A1 (en) 2005-12-28 2008-02-14 Reitz Robert R Process for recycling polyesters
EP1811071A1 (en) 2006-01-18 2007-07-25 Celanese Emulsions GmbH Latex bonded airlaid fabric and its use
US7635745B2 (en) 2006-01-31 2009-12-22 Eastman Chemical Company Sulfopolyester recovery
US7981509B2 (en) 2006-02-13 2011-07-19 Donaldson Company, Inc. Polymer blend, polymer solution composition and fibers spun from the polymer blend and filtration applications thereof
CA2642186A1 (en) 2006-02-13 2007-08-23 Donaldson Company, Inc. Filter web comprising fine fiber and reactive, adsorptive or absorptive particulate
WO2007096242A1 (en) 2006-02-20 2007-08-30 Clariant International Ltd Improved process for the manufacture of paper and board
US7588688B2 (en) 2006-03-03 2009-09-15 Purifics Environmental Technologies, Inc. Integrated particulate filtration and dewatering system
WO2007112443A2 (en) 2006-03-28 2007-10-04 North Carolina State University Micro and nanofiber nonwoven spunbonded fabric
US20070232180A1 (en) 2006-03-31 2007-10-04 Osman Polat Absorbent article comprising a fibrous structure comprising synthetic fibers and a hydrophilizing agent
US7737060B2 (en) 2006-03-31 2010-06-15 Boston Scientific Scimed, Inc. Medical devices containing multi-component fibers
MX2008012228A (en) 2006-03-31 2008-10-02 Procter & Gamble Nonwoven fibrous structure comprising synthetic fibers and hydrophilizing agent.
MX2008012848A (en) 2006-04-07 2008-10-13 Kimberly Clark Co Biodegradable nonwoven laminate.
US20070259029A1 (en) 2006-05-08 2007-11-08 Mcentire Edward Enns Water-dispersible patch containing an active agent for dermal delivery
US20070258935A1 (en) 2006-05-08 2007-11-08 Mcentire Edward Enns Water dispersible films for delivery of active agents to the epidermis
US20070278152A1 (en) 2006-05-31 2007-12-06 Musale Deepak A Method of improving performance of ultrafiltration or microfiltration membrane process in landfill leachate treatment
US20070278151A1 (en) 2006-05-31 2007-12-06 Musale Deepak A Method of improving performance of ultrafiltration or microfiltration membrane processes in backwash water treatment
US20080003400A1 (en) 2006-06-30 2008-01-03 Canbelin Industrial Co., Ltd. Method for making a pile fabric and pile fabric made thereby
US20080000836A1 (en) 2006-06-30 2008-01-03 Hua Wang Transmix refining method
US20080003905A1 (en) 2006-06-30 2008-01-03 Canbelin Industrial Co., Ltd. Mat
US7803275B2 (en) 2006-07-14 2010-09-28 Exxonmobil Research And Engineering Company Membrane separation process using mixed vapor-liquid feed
US7902096B2 (en) 2006-07-31 2011-03-08 3M Innovative Properties Company Monocomponent monolayer meltblown web and meltblowing apparatus
US7858163B2 (en) 2006-07-31 2010-12-28 3M Innovative Properties Company Molded monocomponent monolayer respirator with bimodal monolayer monocomponent media
US7947142B2 (en) 2006-07-31 2011-05-24 3M Innovative Properties Company Pleated filter with monolayer monocomponent meltspun media
KR101423797B1 (en) 2006-08-04 2014-07-25 가부시키가이샤 구라레 Stretch nonwoven fabric and tapes
WO2008028134A1 (en) 2006-09-01 2008-03-06 The Regents Of The University Of California Thermoplastic polymer microfibers, nanofibers and composites
US20100072126A1 (en) 2006-09-22 2010-03-25 Kuraray Co., Ltd. Filter material and method for producing the same
DE102006045616B3 (en) 2006-09-25 2008-02-21 Carl Freudenberg Kg Manufacture of resilient fleece with thermoplastic filaments, places fleece in hot water containing additives, jiggers, tensions, reduces width, dries and winds up
MY148235A (en) 2006-10-11 2013-03-29 Toray Industries Leather- like sheet and production process thereof
US7666343B2 (en) 2006-10-18 2010-02-23 Polymer Group, Inc. Process and apparatus for producing sub-micron fibers, and nonwovens and articles containing same
US8129019B2 (en) 2006-11-03 2012-03-06 Behnam Pourdeyhimi High surface area fiber and textiles made from the same
EP2082082B1 (en) 2006-11-14 2011-07-27 Arkema Inc. Multi-component fibers containing high chain-length polyamides
US8361180B2 (en) 2006-11-27 2013-01-29 E I Du Pont De Nemours And Company Durable nanoweb scrim laminates
US7884037B2 (en) 2006-12-15 2011-02-08 Kimberly-Clark Worldwide, Inc. Wet wipe having a stratified wetting composition therein and process for preparing same
US8865336B2 (en) 2006-12-20 2014-10-21 Kuraray Co., Ltd. Separator for alkaline battery, method for producing the same, and battery
US20080160278A1 (en) 2006-12-28 2008-07-03 Cheng Paul P Fade resistant colored sheath/core bicomponent fiber
ES2533871T3 (en) 2007-02-26 2015-04-15 Hexion Specialty Chemicals Research Belgium S.A. Compositions of resin-polyester blend binder, method of preparation thereof and articles prepared therefrom
US20080233850A1 (en) 2007-03-20 2008-09-25 3M Innovative Properties Company Abrasive article and method of making and using the same
US7628829B2 (en) 2007-03-20 2009-12-08 3M Innovative Properties Company Abrasive article and method of making and using the same
EP2138634B1 (en) 2007-04-17 2012-08-22 Teijin Fibers Limited Wet-laid non-woven fabric and filter
US20100136312A1 (en) 2007-04-18 2010-06-03 Kenji Inagaki Tissue
JP5298383B2 (en) 2007-04-25 2013-09-25 Esファイバービジョンズ株式会社 Heat-adhesive conjugate fiber excellent in bulkiness and flexibility and fiber molded article using the same
WO2008146898A1 (en) 2007-05-24 2008-12-04 Es Fibervisions Co., Ltd. Splittable conjugate fiber, aggregate thereof, and fibrous form made from splittable conjugate fibers
EP2151270A4 (en) 2007-05-31 2011-03-16 Toray Industries Nonwoven fabric for cylindrical bag filter, process for producing the same, and cylindrical bag filter therefrom
KR100971110B1 (en) 2007-06-06 2010-07-20 데이진 가부시키가이샤 Separator for nonaqueous secondary battery and nonaqueous secondary battery
CN101688331A (en) 2007-06-29 2010-03-31 3M创新有限公司 Indicating fiber
US20100133198A1 (en) 2007-07-24 2010-06-03 Herbert Gunther Joachim Langner Method and apparatus for separating waste products from cellulose fibres in a paper recycling process
US8058194B2 (en) 2007-07-31 2011-11-15 Kimberly-Clark Worldwide, Inc. Conductive webs
US7981336B2 (en) 2007-08-02 2011-07-19 North Carolina State University Process of making mixed fibers and nonwoven fabrics
WO2009024836A1 (en) 2007-08-22 2009-02-26 Kimberly-Clark Worldwide, Inc. Multicomponent biodegradable filaments and nonwoven webs formed therefrom
EP2184391B1 (en) 2007-08-31 2016-10-12 Kuraray Co., Ltd. Buffer substrate and use thereof
JP5444681B2 (en) 2007-10-19 2014-03-19 Esファイバービジョンズ株式会社 Polyester-based heat-fusible composite fiber
KR101554052B1 (en) 2007-12-06 2015-09-17 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Electret webs with charge-enhancing additives
UA97720C2 (en) 2007-12-11 2012-03-12 Пи.Эйч. Глетфелтер Компани Plate assembly for lead-acid battery (embodiments) and multilayer composite sheet therefor
US20090163449A1 (en) 2007-12-20 2009-06-25 Eastman Chemical Company Sulfo-polymer powder and sulfo-polymer powder blends with carriers and/or additives
CN101946033B (en) 2007-12-28 2012-11-28 3M创新有限公司 Composite nonwoven fibrous webs and methods of making and using the same
JP5524862B2 (en) 2007-12-31 2014-06-18 スリーエム イノベイティブ プロパティズ カンパニー Composite nonwoven fibrous web having a continuous particulate phase and methods for making and using the same
EP2242726B1 (en) 2007-12-31 2018-08-15 3M Innovative Properties Company Fluid filtration articles and methods of making and using the same
BRPI0819941A2 (en) 2008-01-08 2015-05-26 Du Pont "breathable and waterproof garment and process for producing a water repellent garment"
US8833567B2 (en) 2008-01-16 2014-09-16 Ahlstrom Corporation Coalescence media for separation of water-hydrocarbon emulsions
EP2244876A4 (en) 2008-02-18 2012-08-01 Sellars Absorbent Materials Inc Laminate non-woven sheet with high-strength, melt-blown fiber exterior layers
WO2009119551A1 (en) 2008-03-24 2009-10-01 株式会社クラレ Split leather product and manufacturing method therefor
US8282712B2 (en) 2008-04-07 2012-10-09 E I Du Pont De Nemours And Company Air filtration medium with improved dust loading capacity and improved resistance to high humidity environment
CN102057086B (en) 2008-04-08 2013-05-29 帝人株式会社 Carbon fiber and method for production thereof
FR2929962B1 (en) 2008-04-11 2021-06-25 Arjowiggins Licensing Sas METHOD OF MANUFACTURING A SHEET INCLUDING AN UNDERTHICKNESS OR AN EXCESS THICKNESS AT THE LEVEL OF A RIBBON AND ASSOCIATED SHEET.
EP2279294A1 (en) 2008-05-05 2011-02-02 Avgol Industries 1953 LTD Nonwoven material
CZ2008277A3 (en) 2008-05-06 2009-11-18 Elmarco S.R.O. Process for preparing inorganic nanofibers by electrostatic spinning
CN102027384A (en) 2008-05-13 2011-04-20 研究三角协会 Porous and non-porous nanostructures and application thereof
KR101577318B1 (en) 2008-05-21 2015-12-14 도레이 카부시키가이샤 Method for producing aliphatic polyester resin, and an aliphatic polyester resin composition
KR101593022B1 (en) 2008-05-28 2016-02-11 니혼바이린 가부시기가이샤 Spinning apparatus and apparatus and process for manufacturing nonwoven fabric
US8866052B2 (en) 2008-05-29 2014-10-21 Kimberly-Clark Worldwide, Inc. Heating articles using conductive webs
EP2281080B1 (en) 2008-05-30 2014-03-19 Kimberly-Clark Worldwide, Inc. Nonwoven web comprising polylactic acid fibers
US8470222B2 (en) 2008-06-06 2013-06-25 Kimberly-Clark Worldwide, Inc. Fibers formed from a blend of a modified aliphatic-aromatic copolyester and thermoplastic starch
JPWO2009150874A1 (en) 2008-06-12 2011-11-10 帝人株式会社 Nonwoven fabric, felt and method for producing them
CN102105625B (en) 2008-06-12 2015-07-08 3M创新有限公司 Melt blown fine fibers and methods of manufacture
EP2135984A1 (en) 2008-06-19 2009-12-23 FARE' S.p.A. A process of producing soft and absorbent non woven fabric
EP2292821B1 (en) 2008-06-25 2017-02-15 Kuraray Co., Ltd. Base material for artificial leather and process for producing the same
JPWO2010001872A1 (en) 2008-07-03 2011-12-22 日清紡ホールディングス株式会社 Liquid storage material and storage method
RU2502835C2 (en) 2008-07-10 2013-12-27 Тейджин Арамид Б.В. Method of producing high-molecular weight polyethylene fibres
KR101585906B1 (en) 2008-07-11 2016-01-15 도레이 배터리 세퍼레이터 필름 주식회사 Microporous membranes and methods for producing and using such membranes
EP2305861A4 (en) 2008-07-18 2013-05-15 Toray Industries Polyphenylene sulfide fiber, process for producing the same, wet-laid nonwoven fabric, and process for producing wet-laid nonwoven fabric
US7998311B2 (en) 2008-07-24 2011-08-16 Hercules Incorporated Enhanced surface sizing of paper
US8071205B2 (en) 2008-07-31 2011-12-06 Toray Industries, Inc. Prepreg, preform, molded product, and method for manufacturing prepreg
US7922959B2 (en) 2008-08-01 2011-04-12 E. I. Du Pont De Nemours And Company Method of manufacturing a composite filter media
US20110129510A1 (en) 2008-08-08 2011-06-02 Basf Se Fibrous surface structure containing active ingredients with controlled release of active ingredients, use thereof and method for the production thereof
US20110171890A1 (en) 2008-08-08 2011-07-14 Kuraray Co., Ltd. Polishing pad and method for manufacturing the polishing pad
JP5400330B2 (en) 2008-08-27 2014-01-29 帝人株式会社 Photocatalyst-containing ultrafine fiber and method for producing the same
KR101562276B1 (en) 2008-09-12 2015-10-21 니혼바이린 가부시기가이샤 Separator for lithium ion secondary battery, method for manufacture thereof, and lithium ion secondary battery
US7928025B2 (en) 2008-10-01 2011-04-19 Polymer Group, Inc. Nonwoven multilayered fibrous batts and multi-density molded articles made with same and processes of making thereof
US8409448B2 (en) 2009-01-13 2013-04-02 The University Of Akron Mixed hydrophilic/hydrophobic fiber media for liquid-liquid coalescence
US8267681B2 (en) 2009-01-28 2012-09-18 Donaldson Company, Inc. Method and apparatus for forming a fibrous media
EP2408830B1 (en) 2009-03-20 2015-09-23 Arkema Inc. Polyetherketoneketone nonwoven mats
MX347301B (en) 2009-03-31 2017-04-21 3M Innovative Properties Co Dimensionally stable nonwoven fibrous webs and methods of making and using the same.
MX2011010443A (en) 2009-04-03 2011-10-24 3M Innovative Properties Co Processing aids for olefinic webs, including electret webs.
US8795717B2 (en) 2009-11-20 2014-08-05 Kimberly-Clark Worldwide, Inc. Tissue products including a temperature change composition containing phase change components within a non-interfering molecular scaffold
US20100272938A1 (en) 2009-04-22 2010-10-28 Bemis Company, Inc. Hydraulically-Formed Nonwoven Sheet with Microfibers
FR2944957B1 (en) 2009-04-30 2011-06-10 Ahlstrom Coroporation CELLULOSIC SUPPORT COMPRISING MANNOSE DERIVATIVES SUITABLE FOR FIXING BACTERIA WITH PILIS TYPE 1, APPLICATION TO DISINFECTANT WIPES, IN PARTICULAR
WO2010140853A2 (en) 2009-06-04 2010-12-09 주식회사 코오롱 Sea-island fibres and artificial leather, and a production method therefor
EP2264242A1 (en) 2009-06-16 2010-12-22 Ahlstrom Corporation Nonwoven fabric products with enhanced transfer properties
CN101933788A (en) 2009-06-30 2011-01-05 3M创新有限公司 Surface cleaning product with composite structure and preparation method thereof
RU2414960C1 (en) 2009-07-09 2011-03-27 Федеральное государственное унитарное предприятие "Научно-исследовательский физико-химический институт им. Л.Я. Карпова" Sorption filtering composite material
RU2414950C1 (en) 2009-07-09 2011-03-27 Федеральное государственное унитарное предприятие "Научно-исследовательский физико-химический институт им. Л.Я. Карпова" Filtration material
EP2292309A1 (en) 2009-08-07 2011-03-09 Ahlstrom Corporation Nanofibers with improved chemical and physical stability and web containing nanofibers
EP2461766A4 (en) 2009-08-07 2013-09-18 Zeus Ind Products Inc Prosthetic device including electrostatically spun fibrous layer and method for making the same
US20110039468A1 (en) 2009-08-12 2011-02-17 Baldwin Jr Alfred Frank Protective apparel having breathable film layer
DE102009037565A1 (en) 2009-08-14 2011-02-24 Mavig Gmbh Coated microfiber web and method of making the same
US8428675B2 (en) 2009-08-19 2013-04-23 Covidien Lp Nanofiber adhesives used in medical devices
US20110054429A1 (en) 2009-08-25 2011-03-03 Sns Nano Fiber Technology, Llc Textile Composite Material for Decontaminating the Skin
CN102482799B (en) 2009-09-01 2016-03-16 3M创新有限公司 For the formation of equipment, the system and method for nanofiber and nanometer fiber net
CN102482843B (en) 2009-09-03 2014-06-18 东丽株式会社 Pilling-resistant artificial leather
KR20120094901A (en) 2009-09-15 2012-08-27 킴벌리-클라크 월드와이드, 인크. Coform nonwoven web formed from meltblown fibers including propylene/alpha-olefin
US20110084028A1 (en) 2009-10-09 2011-04-14 Ahlstrom Corporation Separation media and methods especially useful for separating water-hydrocarbon emulsions having low interfacial tensions
US9935302B2 (en) 2009-10-20 2018-04-03 Daramic, Llc Battery separators with cross ribs and related methods
AU2010308287B2 (en) 2009-10-21 2013-09-19 3M Innovative Properties Company Porous supported articles and methods of making
KR20120079842A (en) 2009-10-21 2012-07-13 쓰리엠 이노베이티브 프로퍼티즈 캄파니 Porous multilayer articles and methods of making
US8528560B2 (en) 2009-10-23 2013-09-10 3M Innovative Properties Company Filtering face-piece respirator having parallel line weld pattern in mask body
DE102009050447A1 (en) 2009-10-23 2011-04-28 Mahle International Gmbh filter material
WO2011052173A1 (en) 2009-10-30 2011-05-05 株式会社クラレ Polishing pad and chemical mechanical polishing method
ES2464128T3 (en) 2009-11-02 2014-05-30 The Procter & Gamble Company Fibrous polypropylene elements and manufacturing processes
US20120283828A1 (en) 2009-11-05 2012-11-08 Nonwotecc Medical Gmbh Non-woven fabric for medical use and process for the preparation thereof
US20110117353A1 (en) 2009-11-17 2011-05-19 Outlast Technologies, Inc. Fibers and articles having combined fire resistance and enhanced reversible thermal properties
US20110252970A1 (en) 2009-11-19 2011-10-20 E. I. Du Pont De Nemours And Company Filtration Media for High Humidity Environments
US9181465B2 (en) 2009-11-20 2015-11-10 Kimberly-Clark Worldwide, Inc. Temperature change compositions and tissue products providing a cooling sensation
JP5792738B2 (en) 2009-11-23 2015-10-14 スリーエム イノベイティブ プロパティズ カンパニー Method for surface treatment of porous particles
JP5774020B2 (en) 2009-11-24 2015-09-02 スリーエム イノベイティブ プロパティズ カンパニー Articles and methods using shape memory polymers
KR20110059541A (en) 2009-11-27 2011-06-02 니혼바이린 가부시기가이샤 Spinning apparatus, apparatus and process for manufacturing nonwoven fabric, and nonwoven fabric
FR2953531B1 (en) 2009-12-07 2012-03-02 Ahlstroem Oy NON-WOVEN SUPPORT FOR JOINT STRIP AND STABLE, DIMENSIONALLY STABLE SEALING STRIP WITHOUT LOSS OF MECHANICAL STRENGTH COMPRISING SAID SUPPORT
FR2956671B1 (en) 2010-02-23 2012-03-30 Ahlstroem Oy CELLULOSIC FIBER SUPPORT CONTAINING MODIFIED PVA LAYER - PROCESS FOR THE PRODUCTION AND USE
ES2523728T3 (en) 2010-06-15 2014-12-01 Ahlstrom Corporation Scrubbed fibrous support containing apergaminable synthetic fibers and method of manufacture

Patent Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3018272A (en) 1955-06-30 1962-01-23 Du Pont Sulfonate containing polyesters dyeable with basic dyes
US3075952A (en) 1959-01-21 1963-01-29 Eastman Kodak Co Solid phase process for linear superpolyesters
US3033822A (en) 1959-06-29 1962-05-08 Eastman Kodak Co Linear polyesters of 1, 4-cyclohexane-dimethanol and hydroxycarboxylic acids
US3528947A (en) 1968-01-03 1970-09-15 Eastman Kodak Co Dyeable polyesters containing units of an alkali metal salts of an aromatic sulfonic acid or ester thereof
US3779993A (en) 1970-02-27 1973-12-18 Eastman Kodak Co Polyesters and polyesteramides containing ether groups and sulfonate groups in the form of a metallic salt
US4304901A (en) 1980-04-28 1981-12-08 Eastman Kodak Company Water dissipatable polyesters
US5281306A (en) 1988-11-30 1994-01-25 Kao Corporation Water-disintegrable cleaning sheet
US4966808A (en) 1989-01-27 1990-10-30 Chisso Corporation Micro-fibers-generating conjugate fibers and woven or non-woven fabric thereof
US5290631A (en) 1991-10-29 1994-03-01 Rhone-Poulenc Chimie Hydrosoluble/hydrodispersible polyesters and sizing of textile threads therewith
US5292581A (en) 1992-12-15 1994-03-08 The Dexter Corporation Wet wipe
US5525282A (en) 1993-03-31 1996-06-11 Basf Corporation Process of making composite fibers and microfibers
US5405698A (en) 1993-03-31 1995-04-11 Basf Corporation Composite fiber and polyolefin microfibers made therefrom
US5366804A (en) 1993-03-31 1994-11-22 Basf Corporation Composite fiber and microfibers made therefrom
US5853701A (en) 1993-06-25 1998-12-29 George; Scott E. Clear aerosol hair spray formulations containing a sulfopolyester in a hydroalcoholic liquid vehicle
US5486418A (en) 1993-10-15 1996-01-23 Kuraray Co., Ltd. Water-soluble heat-press-bonding polyvinyl alcohol binder fiber of a sea-islands structure
US5509913A (en) 1993-12-16 1996-04-23 Kimberly-Clark Corporation Flushable compositions
US5543488A (en) 1994-07-29 1996-08-06 Eastman Chemical Company Water-dispersible adhesive composition and process
US5570605A (en) 1994-09-13 1996-11-05 Kanzaki Kokyukoki Mfg. Co., Ltd. Transmission assembly for tractors
US5916678A (en) 1995-06-30 1999-06-29 Kimberly-Clark Worldwide, Inc. Water-degradable multicomponent fibers and nonwovens
US5935880A (en) 1997-03-31 1999-08-10 Wang; Kenneth Y. Dispersible nonwoven fabric and method of making same
US6552162B1 (en) 1997-07-31 2003-04-22 Kimberly-Clark Worldwide, Inc. Water-responsive, biodegradable compositions and films and articles comprising a blend of polylactide and polyvinyl alcohol and methods for making the same
US6211309B1 (en) 1998-06-29 2001-04-03 Basf Corporation Water-dispersable materials
US6171685B1 (en) 1999-11-26 2001-01-09 Eastman Chemical Company Water-dispersible films and fibers based on sulfopolyesters
WO2001066666A2 (en) 2000-03-09 2001-09-13 Ato Findley, Inc. Sulfonated copolyester based water-dispersible hot melt adhesive
US6428900B1 (en) 2000-03-09 2002-08-06 Ato Findley, Inc. Sulfonated copolyester based water-dispersible hot melt adhesive
US6548592B1 (en) 2000-05-04 2003-04-15 Kimberly-Clark Worldwide, Inc. Ion-sensitive, water-dispersible polymers, a method of making same and items using same
WO2007089423A2 (en) 2006-01-31 2007-08-09 Eastman Chemical Company Water-dispersible and multicomponent fibers from sulfopolyesters
WO2008085332A2 (en) * 2007-01-03 2008-07-17 Eastman Chemical Company Nonwovens fabrics produced from multicomponent fibers comprising sulfopolyesters

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
D.R. PAUL AND C.B. BUCKNALL,: "Polymer Blends", vol. 1, 2, 2000, JOHN WILEY & SONS, INC.

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CN103476988A (en) * 2010-10-21 2013-12-25 伊士曼化工公司 Nonwoven article with ribbon fibers
JP2013545838A (en) * 2010-10-21 2013-12-26 イーストマン ケミカル カンパニー Nonwoven products with ribbon fibers
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