WO2010123580A1 - Sulfopolyesters for paper strength and process - Google Patents

Sulfopolyesters for paper strength and process Download PDF

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Publication number
WO2010123580A1
WO2010123580A1 PCT/US2010/001216 US2010001216W WO2010123580A1 WO 2010123580 A1 WO2010123580 A1 WO 2010123580A1 US 2010001216 W US2010001216 W US 2010001216W WO 2010123580 A1 WO2010123580 A1 WO 2010123580A1
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WO
WIPO (PCT)
Prior art keywords
fibers
resins
sulfopolyester
paper products
residues
Prior art date
Application number
PCT/US2010/001216
Other languages
French (fr)
Inventor
Rakesh Kumar Gupta
Daniel William Klosiewicz
Melvin Glenn Mitchell
Narvin Lynn 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 BRPI1014169A priority Critical patent/BRPI1014169A2/en
Priority to CN201080018994.XA priority patent/CN102414369B/en
Priority to EP10767439.2A priority patent/EP2422012A4/en
Priority to JP2012507220A priority patent/JP5805076B2/en
Publication of WO2010123580A1 publication Critical patent/WO2010123580A1/en

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Classifications

    • 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
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/28Polyesters
    • 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/46Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/58Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur
    • 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
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18Reinforcing agents
    • 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
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18Reinforcing agents
    • D21H21/20Wet strength agents

Definitions

  • This invention provides a method of improving the wet-strength of cellulosic paper while enhancing the repulpability.
  • wet strength resins are often added to paper products including paperboard at the time of manufacture. In the absence of wet strength resins, paper normally retains only 3% to 5% of its strength after being wetted with water. However, paper made with wet strength resin generally retains at least 10%-50% of its strength when wet. Wet strength is useful in a wide variety of paper applications, some examples of which are toweling, milk and juice cartons, paper bags, and liner board for corrugated containers.
  • Paper has traditionally been defined as a felted sheet formed on a fine screen from a water suspension of fibers. Current paper products generally conform to this definition except that most products also contain non-fibrous additives. Dry forming methods are now utilized for the manufacture of a few specialty paper products. Pulp is the fibrous raw material for papermaking. Pulp fibers are usually of vegetable origin, but animal, mineral, or synthetic fibers may be used for special applications. The distinction between paper and paperboard is based on product thickness. Nominally, all sheets above 0.3 mm thickness are classed as paperboard; but enough exceptions are applied to make the distinction somewhat hazy.”
  • the present invention relates to repulpable paper products comprising: papermaking fibers; cationic strength additives; and sulfopolyester thermoplastic resins.
  • the present invention also relates to methods of improving the wet- strength of paper which comprises adding to the paper during the papermaking process cationic strength additives; and sulfopolyester thermoplastic resins.
  • the present invention relates to paper products comprising: papermaking fibers; cationic strength additives; and sulfopolyester thermoplastic resins.
  • the present invention relates to methods of improving the wet-strength of cellulosic paper comprising adding to the papermaking fibers during the papermaking process cationic strength additives and sulfopolyester thermoplastic resins.
  • Optional or optionally means that the subsequently described events or circumstances may or may not occur.
  • the description includes instances where the events or circumstances occur, and instances where they do not occur.
  • ranges stated in this disclosure and the claims are intended to include the entire range specifically and not just the endpoint(s).
  • 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.
  • Papermaking fibers include all known cellulosic fibers or fiber mixes comprising cellulosic fibers.
  • Fibers suitable for making the webs of this invention comprise any natural or synthetic cellulosic fibers including, but not limited to non-woody fibers, such as cotton or cotton derivatives, abaca, kenaf, sabai grass, flax, esparto grass, straw, jute hemp, bagasse, milkweed floss fibers, and pineapple leaf fibers; and woody fibers such as those obtained from deciduous and coniferous trees, including softwood fibers, such as northern and southern softwood kraft fibers; hardwood fibers, such as eucalyptus, maple, birch, and aspen.
  • non-woody fibers such as cotton or cotton derivatives, abaca, kenaf, sabai grass, flax, esparto grass, straw, jute hemp, bagasse, milkweed floss fibers, and pineapple leaf fibers
  • woody fibers such as those obtained from deciduous and coniferous trees, including softwood fibers, such as northern and southern softwood kraft fiber
  • Woody fibers may be prepared in high-yield or low-yield forms and may be pulped in any known method, including kraft, sulfite, groundwood, thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), and bleached chemithermomechanical pulp (BCTMP), high-yield pulping methods and other known pulping methods.
  • High brightness pulps including chemically bleached pulps, may be used and unbleached or semi- bleached pulps may also be used.
  • Recycled fibers are included within the scope of the present invention. Any known pulping and bleaching methods may be used. Fibers prepared from organosolv pulping methods may also be used. Suitable papermaking fibers may also include recycled fibers, virgin fibers, or mixes thereof.
  • Synthetic cellulose fibers are also suitable for use including rayon in all its varieties and other fibers derived from viscose or chemically modified cellulose.
  • Chemically treated natural cellulosic fibers may be used such as mercerized pulps, chemically stiffened or crosslinked fibers, sulfonated fibers, and the like.
  • Suitable synthetic polymeric fibers include rayon, polyolefin fibers, polyester fibers, polyamide fibers and the like.
  • Suitable synthetic polymer fiber structures include monocomponent , bicomponent, and multi component fibers such as core-sheath, islands-in-the-sea, side-by-side, segmented pie, and the like.
  • the papermaking fibers comprise woody fibers, softwood Kraft pulp, hardwood Kraft pulp, recycled fibers, non-woody fibers, synthetic polymeric fibers, glass fibers, or combinations thereof.
  • the synthetic polymeric fibers have a mean fiber diameter of less than 5 microns.
  • the synthetic polymeric fibers comprise greater than 50% of the total papermaking fiber or greater than 70% of the total papermaking fiber.
  • the fibers be relatively undamaged and largely unrefined or only lightly refined. While recycled fibers may be used, virgin fibers are also useful for their mechanical properties and lack of contaminants. Mercerized fibers, regenerated cellulosic fibers, cellulose produced by microbes, rayon, and other cellulosic material or cellulosic derivatives may be used. Suitable papermaking fibers may also include recycled fibers, virgin fibers, or mixes thereof.
  • high yield Pulp fibers are those papermaking fibers of pulps produced by pulping processes providing a yield of about 65 percent or greater. Yield is the resulting amount of processed fiber expressed as a percentage of the initial wood mass.
  • High yield pulps include bleached chemithermomechanical pulp (BCTMP), chemithermomechanical pulp (CTMP) pressure/pressure thermomechanical pulp (PTMP), thermomechanical pulp (TMP), thermomechanical chemical pulp (TMCP), high yield sulfite pulps, and high yield Kraft pulps, all of which contain fibers having high levels of lignin. Characteristic high-yield fibers can have lignin content by mass of about 1 percent or greater.
  • Suitable high yield pulp fibers after being prepared by pulping and optional bleaching steps and prior to being formed into dry bales or webs, in one embodiment can also be characterized by being comprised of comparatively whole, relatively undamaged fibers, high freeness (250 Canadian Standard Freeness (CSF) or greater, and low fines content (less than 25 percent by the Britt jar test).
  • the high-yield fibers are predominately softwood, for example northern softwood.
  • the term "cellulosic” is meant to include any material having cellulose as a major constituent, and specifically comprising about 50 percent or more by weight of cellulose or cellulose derivatives.
  • the term includes cotton, typical wood pulps, non-woody cellulosic fibers, cellulose acetate, cellulose triacetate, rayon, viscose fibers, thermomechanical wood pulp, chemical wood pulp, debonded chemical wood pulp, lyocell and other fibers formed from solutions of cellulose in NMMO, milkweed, or bacterial cellulose. Fibers that have not been spun or regenerated from solution may be used exclusively, if desired, or at least about 80% of the web may be free of spun fibers or fibers generated from a cellulose solution.
  • One aspect of the present invention relates to the production of paper products including paper and paper board from an aqueous slurry of papermaking fibers. It was discovered that the paper products of the present invention containing a cationic strength additive and a sulfopolyester thermoplastic resin resulted in paper products with improved or maintained wet strength and dry strength and with significantly enhanced repulpability.
  • One embodiment of the present invention relates to repulpable paper product comprising: papermaking fibers; cationic strength additives; and thermoplastic sulfopolyester resins.
  • Another embodiment of the present invention relates to paper product comprising: papermaking fibers; cationic strength additives; and thermoplastic sulfopolyester resins.
  • the paper products according the present invention provide enhance repulpability.
  • the paper products according to the present invention also provide enhanced sheet strength, increased machine speed, and improved retention.
  • the present invention also allows the papermakers to simplify the wet end by reducing or eliminating the use of certain wet end additives, including dry strength resins, cationic starches, drainage and retention aids, and coagulants. When the present invention is used as both a wet and dry strength aid, the absorbency of the paper product is not decreased.
  • the present invention provides the following improvements in sheet performance: lower basis weight, increased recycle fiber utilization, the ability to provide dispersion at higher concentration or in solid form, extended shelf life, reduced Kraft utilization, immediate cure, improved print receptivity, improved surface strength, improved sheet processibility, improved machine runnability, increased production, higher sheet ash content and filler cost savings, improved fiber recovery, reduced Whitewater solids and turbidity, increased retention of wet strength additive, reduced system deposition, provides high levels of controllable drainage, improved formation, increased machine speed, reduced dryer energy consumption, simplified and cleaner wet end resulting from fewer additives, cost-effective additive scheme, and wet end chemical efficiency gains.
  • the process of the present invention includes providing a slurry of papermaking fibers, adding the components of the present invention to the slurry of pulp papermaking fibers, depositing the slurry of pulp papermaking fibers containing the components of the present invention on a forming fabric, and drying the slurry to form a paper web.
  • the fibrous web to be formed from the papermaking fibers treated in accordance with the present invention may be wet-laid, such as webs may be formed with known papermaking techniques wherein the dilute aqueous fiber slurry is disposed on a moving wire to filter out the fibers and form a paper web which is subsequently dewatered by combinations of units including suction boxes, wet presses, dryer units, and the like. Capillary dewatering may also be applied to remove water from the web.
  • Drying operations may include drum drying, through drying, steam drying such as superheated steam drying, displacement dewatering, Yankee drying, infrared drying, microwave drying, radio frequency drying in general, and impulse drying.
  • a moist fibrous web may also be formed by foam forming processes, wherein the treated fibers are entrained or suspended in a foam prior to dewatering, or wherein foam is applied to a paper web prior to dewatering or drying.
  • the fibrous web is generally a random plurality of papermaking fibers that can, optionally, be joined together with a binder. Any papermaking fibers, as herein defined, or mixtures thereof may be used, such as bleached fibers from a kraft or sulfite chemical pulping process. Recycled fibers may also be used, as may cotton linters or papermaking fibers comprising cotton. Both high- yield and low-yield fibers may be used.
  • the fibers may be predominantly hardwood, such as at least 50% hardwood or about 60% hardwood or greater or about 80% hardwood or greater or substantially 100% hardwood.
  • the web is predominantly softwood, such as at least about 50% softwood or at least about 80% softwood, or about 100% softwood.
  • the web is predominantly synthetic polymeric fiber, such as at least about 50% synthetic polymeric fiber or at least about 80% synthetic polymeric fiber, or about 100% synthetic polymeric fiber.
  • the fibrous web of the present invention may be formed from a single layer or multiple layers. Stratified webs may also be formed wherein at least one layer comprises softwood fibers while another layer comprises hardwood or other fiber types. Layered structures produced by any means known in the art are within the scope of the present invention. In the case of multiple layers, the layers are generally positioned in a juxtaposed or surface-to-surface relationship and all or a portion of the layers may be bound to adjacent layers.
  • the paper web may also be formed from a plurality of separate paper webs wherein the separate paper webs may be formed from single or multiple layers.
  • One embodiment of the present invention provides a method of improving the wet-strength of a cellulosic paper which comprises adding to the paper during the papermaking process a cationic strength additive; and a sulfopolyester thermoplastic resin.
  • the process for manufacturing paper products or the repulpable paper products according to the present invention comprises a number of steps.
  • One step comprises forming an aqueous slurry of papermaking fibers or pulp or which can be performed by conventional means, i.e., known mechanical, chemical and semi-chemical, etc., pulping processes.
  • Another step comprises adding to the aqueous slurry of papermaking fibers or pulp cationic strength additives and thermoplastic sulfopolyester resins. This can be done at any point, before sheet formation or it can also be applied after sheet formation from a tub size or at a size press or from showers to the dried or partially dried sheet.
  • Yet another step comprises sheeting and drying the aqueous slurry of papermaking or pulp fibers containing the cationic thermosetting resin. This can be done by any conventional means.
  • the components of the present invention comprising the cationic strength additives and the thermoplastic sulfopolyester resins are added to the pulp slurry separately, though depending on desired strength characteristics of the web, either the cationic strength additives or the thermoplastic sulfopolyester resins may be added to the slurry before the other.
  • the cationic strength additive can be incorporated by various methods including addition in the pulp fiber slurry or incorporation at the pulp press.
  • the cationic strength additives are added to the slurry before the sulfopolyester thermoplastic resin.
  • the cationic strength additive bonds to the anionically charged cellulose pulp fibers which results in a positively charged pulp fiber.
  • the anionically charged sulfopolyester thermoplastic resin is applied to pulp fiber which results in an ionic bond.
  • the sulfopolyester resin can be applied by various methods including spray application.
  • the process of the present invention includes providing a slurry of pulp or papermaking fibers, sequentially adding the components of the present invention to the aqueous slurry of pulp or papermaking fibers, depositing the slurry of pulp or papermaking fibers containing the components of the present invention on a forming fabric, and drying the slurry to form a paper web.
  • Such components may also be sprayed, printed, or coated onto the web after formation, while wet, or added to the wet end of the papermaking machine prior to formation.
  • the components comprising the cationic strength additives and the thermoplastic sulfopolyester resins may be added to the slurry in a ratio from about a 1 :5 to about a 5:1, as desired.
  • the pH of the slurry may be adjusted during the process.
  • the pH of the slurry may be adjusted to an acidic pH, such as about 6 or less in one embodiment. In another embodiment, however, the pH may be adjusted to greater than about 6.
  • sufficient water is then added to adjust the solids content of the resin solution to about 15% or less, the product cooled to about 25° C. and then stabilized by adding sufficient acid to reduce the pH at least to about 6 and preferably to about 5.
  • Any suitable acid such as hydrochloric, sulfuric, nitric, formic, phosphoric and acetic acid may be used to stabilize the product.
  • the paper web of the present invention may have any conventional bulk weight.
  • the paper web of the present invention may have a bulk greater than about 2 cc/g.
  • the paper web may have a bulk greater than about 5 cc/g.
  • the dry tensile index of the paper web may be any conventional value.
  • the dry tensile index of the paper web can be greater than about 20 Nm/g in one embodiment.
  • the dry tensile index of the paper web can be greater than about 22 Nm/g.
  • the dry tensile index can be greater than about 25 Nm/g.
  • the basis weight of the paper webs of the present invention can be any desired basis weight.
  • the paper web may have a basis weight between about 5 and about 200 gsm.
  • rosin size reactive size (alkenyl succinic anhydride or alkyl ketene dimer), surface size, starch, retention aids, drainage aids, formation aids, flocculants, creping aids (adhesives and release agents), dry strength resins (cationic starch, guar gums, polyacrylamides), defoamers, scavengers for anionic trash and stickies control, fillers (clay, calcium carbonate, titanium dioxide), optical brightening aids and dyes.
  • chemical additives are often incorporated to improve the wet strength and/or dry strength of paper and paperboard products.
  • These chemical additives are commonly known as wet and dry strength additives and are available from a number of commercially available sources.
  • Examples of permanent wet strength additives include polyamide epichlorohydrin and polyamidoamine epichlorohydrin and are collectively known as PAE resins.
  • Examples of wet strength additives are based on chemistries such as polyacrylamide and glyoxalated polyacrylamide (GPAM) resins.
  • the cationic strength additives may consist of either wet strength or dry strength additives and include glyoxylated polyacrylamides, polyacrylamides, polyamide epichlorohydrins (PAEs), starches and other cationic additives well known to those skilled in the art.
  • PAE resins Polyamide epichlorohydrin, polyamidoamine epichlorohydrin and polyamine epichlorohydrin resins and are collectively known as PAE resins.
  • PAE resins are widely used in the papermaking industry due to their ability to impart a high degree of wet strength to numerous paper products, including tissue, towel, wipes and corrugated board.
  • PAE resins do not improve the dry strength of paper or paperboard and products containing these resins are generally considered not to be repulpable. Paper products containing wet strength additives, although generally repulpable; often have insufficient wet strength for many applications. Upon complete wetting, paper products derived from wet strength additives typically degrade within minutes to hours.
  • Suitable cationic strength additives used in accordance with the present invention include PAE resins, glyoxylated polyacrylamide resins, starches, polyacrylamides, and other wet strength and dry strength additives commonly known to those skilled in the art.
  • PAE resins Procedures for making PAE resins are well known in the literature and are described in more detail in U.S. Pat. No. 3,772,076, which is incorporated herein by reference.
  • PAE resins are sold by Ashland, Inc., Wilmington, Delaware, under the trade name Kymene® and by Georgia Pacific, Inc., Atlanta, Georgia, under the trade name Amres®.
  • a typical procedure for synthesizing a PAE resin is as follows.
  • a polyalkylene polyamine is reacted with an aliphatic dicarboxylic acid to form a polyamidoamine backbone.
  • An example of a polyamidoamine is the reaction product of diethyl enetriamine with an adipic acid or ester of a dicarboxylic acid derivative.
  • the resulting polyamidoamine is then reacted with epichlorohydrin in aqueous solution.
  • the resulting product is diluted and neutralized with a strong mineral acid to a pH below 3.0.
  • Glyoxylated polyacrylamide resins are sold by Kemira, Inc., Kennesaw, Georgia, under the trade name Parez®.
  • the acrylamide polymer may contain monomers to modify ionic properties.
  • the acrylamide base polymer is reacted with sufficient glyoxal under aqueous alkaline conditions until a slight increase in viscosity occurs.
  • the resulting product is then quenched with acid. Approximately half of the added glyoxyal remains unreacted and dissolved in the water.
  • Dry strength additives include materials such as starches that may be cationic, quaternary or nonionic in nature.
  • dry strength additives suitable for use in the present invention include cationic derivatives of polysaccharides (such as starch, guar, cellulose, and chitin); polyamine; polyethyleneimine; vinylalcohol-vinylamine copolymers; cationic acrylic homo- and copolymers such as polyacrylamide, polydiallyldimethylammonium chloride and copolymers of acrylic acid, acrylic esters and acrylamide with diallyldimethylammonium chloride, acryloyloxyethyltrimethylammoniurn chloride, methacryloyloxyethyltrimethylammonium methylsulfate, methacryloyloxyethyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride.
  • polysaccharides such as starch, guar, cellulose, and chitin
  • polyamine polyethyleneimine
  • cationic strength resins that may be used in the present invention are: aminopolyamide-epi resins (e.g. Kymene® 557H-resin); polyamine-epi resins (e.g. Kymene® 736 resin), epoxide resins (e.g. Kymene® 450 and Kymene® 2064 resins); polyethylenimine, ureaformaldehyde resins; melamine- formaldehyde resins; glyoxalated polyacrylamides (e.g. Hercobond® 1000 resin, Parez 63 INC); polyisocyanates; and reactive starches (oxidized starch, dialdehyde starch, blocked reactive group starch).
  • aminopolyamide-epi resins e.g. Kymene® 557H-resin
  • polyamine-epi resins e.g. Kymene® 736 resin
  • epoxide resins e.g. Kymene® 450 and Ky
  • the amount of cationic strength additive is generally from about 0.25 to about 3.00 weight % on a dry basis, based on the weight of the dried paper.
  • the amount of cationic strength additive is from about 0.25-3.00 weight percent, 0.25-2.00 weight percent, or 0.25-1.50 weight percent.
  • the cationic strength additive may be about 2 weight % on a dry basis, based on the weight of the dried paper, or about 1 weight %, or about 0.5 weight %.
  • similar amounts of wet strength additive and sulfopolyester are used.
  • the sulfopolyesters of the present invention comprisedicarboxylic 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 sulfopolyeseter 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 sulfopolyeseter 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. degree. C. and at a concentration of about 0.5 g of sulfopolyester in 100 mL of solvent.
  • polyyester encompasses both “homopolyesters” and “copolyesters” and means a synthetic polymer prepared by the polycondensation of difunctional carboxylic acids with difunctional hydroxyl compound.
  • the term "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, 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.
  • 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-norbomanedicarboxylic; 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- 1 ,4-cyclohexane-dicarboxylate 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, hi 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.
  • sulfonate refers to a salt of a sulfonic acid having the structure "-SO.sub.3M" wherein M is the cation of the sulfonate salt.
  • the cation of the sulfonate salt may be a metal ion such as Li.sup.+, Na.sup.+, K.sup.+, Mg.sup.++, Ca.sup.++, Ni.sup.++, Fe.sup.++, 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. Pat. No. 4,304,901.
  • Nitrogen-based cations are derived from nitrogen-containing bases, which may be aliphatic, cycloaliphatic, or aromatic compounds.
  • 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 0.4 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 sulfopolyesters 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. Pat. Nos. 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 ethylene glycol; diethylene glycol; triethylene glycol; polyethylene glycols; 1,3-propanediol; 2,4-dimethyl-2-ethylhexane-l,3- diol; 2,2-dimethyl-l,3-propanediol; 2-ethyl-2-butyl-l,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-
  • 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-- (OCH.sub.2— CH.sub.2).sub.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 diethyl ene glycol, triethylene glycol, and tetraethylene glycol. Of these lower molecular weight glycols, diethylene and triethylene glycol are most preferred.
  • PEG polyethylene glycols
  • CARBOWAX.RTM a product of Dow Chemical Company (formerly Union Carbide).
  • PEG's are used in combination with other 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 sulfopolyesters of the present invention has a glass transition temperature, abbreviated herein as "Tg", of at least 25. degree. C. as measured on the dry polymer using standard techniques, such as differentical 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.degree. 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 30.degree. C, at least 35.degree. C, at least 40. degree. C, at least 5O.degree. C, at least 60. degree. C, at least 65. degree. C, at least 80. degree. C, and at least 9O.degree. C.
  • typical glass transition temperatures of the dry sulfopolyesters our invention are about 30.degree. C, about 48. degree. C, about 55. degree. C, about 65.degree. C, about 7O.degree. C, about 75.degree. C, about 85. degree. C, and about 9O.degree. C.
  • Our invention also provides sulfopolyesters which comprise: (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-- (OCH.sub.2-- CH.sub.2).sub.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.
  • 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".
  • 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 are about 10 to about 75 mole %, about 25 to about
  • 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 present 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. 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.
  • 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. Pat. Nos.
  • 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. 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 15O.degree. C. to about 25O.degree. C.
  • the temperature for the ester interchange reaction ranges from about 180.degree. C. to about 230.degree. 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).
  • 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 23O.degree. C. to about 350.degree. C, preferably about 250.degree. C. to about 310.degree. C. and most preferably about 26O.degree. C. to about 29O.degree. 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.
  • 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. Pat. 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 180.degree. C. to about 280. degree. C, more preferably ranging from about 22O.degree. C. to about 27O.degree. C.
  • This low molecular weight polymer may then be polymerized by a polycondensation reaction.
  • the amount of thermoplastic sulfopolyester resin is generally from about 0.25 to about 3.00 weight % on a dry basis, based on the weight of the dried paper. For example in one embodiment the amount of sulfopolyester is from about 0.25-3.00 weight percent, 0.25-2.00 weight percent, or 0.25-1.50 weight percent . In another embodiment the amount of thermoplastic sulfopolyester can be about 0.05 weight % on a dry basis, or about 0.1 weight % or about 0.2 weight %. Typically the ratio of thermoplastic sulfopolyester resin to cationic strength additive is about 5:1 to about 1 :5. hi one embodiment the ratio of f sulfopolyester to cationic strength additive is about 1 :1.
  • the repulping process may be carried out using any conventional method.
  • the process of repulping the paper to obtain recycled pulp fibers can be carried out by any mechanical action that disperses dry pulp fibers into an aqueous pulp fiber suspension.
  • Conditions for repulping, as well as equipment commercially used, are discussed in "Handbook for Pulp & Paper Technologists, Second Edition" by G. A. Smook, Angus Wilde Publications, 1992, pp 194-195 and 211-212, which reference is incorporated herein by reference in its entirety.
  • paper prepared by the process of the present invention can be repulped in substantially less time than is required to repulp the same paper at about the same level of wet-strength.
  • the paper products of the present invention are suitable for use in the following areas: paper towels; napkins; facial tissue; liquid packaging board (milk carton, juice carton); poultry boxes; produce boxes; ca ⁇ erboard; butchers wrap; bleached bag; poster board; table cloth; wallboard tape; currency paper; map paper; tea bag; corrugating medium; paper plates; molded products (egg cartons); laminating grades; flooring felt; coffee filter; bread wrap; multiwall bag; shingle wrap, etc.
  • the recycled pulp fibers prepared by the repulping process of the present invention can be used to make paper by conventional paper making processes, which comprise providing an aqueous suspension of the recycled pulp fibers and then sheeting and drying the aqueous suspension to obtain paper.
  • conventional paper making processes which comprise providing an aqueous suspension of the recycled pulp fibers and then sheeting and drying the aqueous suspension to obtain paper.
  • a 3 wt% solution of a sulfopolyester was prepared as follows. 500 grams of distilled water was placed into a beaker heated to approximately 88.degrees.C on a hot plate. 15.5 grams of sulfopolyester pellets were added and continually stirred while maintaining a temperature of 88.degrees.C F for 10-15 minutes or until all of the sulfopolyester had dissolved. The mixture was cooled and distilled water was added to achieve a total solution weight of 515.5 grams.
  • a 3 wt% solution of a PAE solution was prepared as follows. 500 grams of distilled water was placed into a beaker. 160 grams of a 12.5 wt% solution of a commercially available PAE solution was added to the beaker and stirred. Coating procedure:
  • Each of the 3 wt% solutions was diluted, respectively, using distilled water such that when 3 ml of the solution was applied to the paper sheet, the target add-on concentration of 0.5 wt% was achieved.
  • a control was prepared as follows. 5 ml of distilled water was added to the paper sheet using a 5 ml volumetric pipette. The water was gently rolled into the sheet using a 2 inch rubber hand roller. The paper sheet, with the release sheet attached, was dried for 5 minutes in a 93.degree.C convection oven. The dried sheet was stored for 4 days under a 2 pound flat weight. This sample is referred to as the Control.
  • a sample containing 0.5 wt% PAE resin was prepared as follows. 5 ml of distilled water was added to the paper sheet using a 5 ml volumetric pipette. The water was gently rolled into the sheet using a hand roller. 3 ml of the diluted PAE solution was added with a 3 ml syringe to the pre-wetted paper. The solution was gently rolled into the sheet using a hand roller until uniform color was achieved. The paper sheet, with the release sheet attached, was dried for 5 minutes in a 93.degree.C convection oven. The dried sheet was stored for
  • Sample 1 A sample containing 0.5 wt% sulfopolyester resin was prepared as follows.
  • An example of the present invention containing 0.25 wt% PAE and 0.25 wt% sulfopolyester was prepared as follows. 5 ml of distilled water was added to the paper sheet using a 5 ml volumetric pipette. The water was gently rolled into the sheet using a hand roller. 3 ml of the diluted PAE solution was added with a 3 ml syringe to the pre-wetted paper. The solution was gently rolled into the sheet using a hand roller until uniform color was achieved. The sheet was allowed to sit for 2 minutes. 3 ml of the diluted sulfopolyester solution was subsequently added to the paper with a 3 ml syringe.
  • Sample 3 The control and Samples 1 , 2 and 3 were evaluated for dry strength and wet strength using the following TAPPI test methods:
  • the repulpability of the paper samples was determined as follows.
  • a brass hydropulper manufactured by Hermann Manufacturing Company was used for testing.
  • the hydropulper was a 2 liter vessel with a 3000 rpm, 3 A horsepower tri-rotor.
  • the hydropulper had a diameter of 6 inches and a height of 10 inches.

Abstract

Sulfopolyester thermoplastic resins provide advantages in papermaking processes and in paper products including paperboard. Improvements in wet strength and dry strength of paper products are achieved by addition of sulfopolyester thermoplastic resins and cationic strength additives during the paper making process. The use of sulfopolyester thermoplastic resins in paper products also significantly enhances the repulpability of the paper.

Description

SULFOPOLYESTERS FOR PAPER STRENGTH AND PROCESS
FIELD OF THE INVENTION This invention provides a method of improving the wet-strength of cellulosic paper while enhancing the repulpability.
BACKGROUND OF THE INVENTION
Wet strength resins are often added to paper products including paperboard at the time of manufacture. In the absence of wet strength resins, paper normally retains only 3% to 5% of its strength after being wetted with water. However, paper made with wet strength resin generally retains at least 10%-50% of its strength when wet. Wet strength is useful in a wide variety of paper applications, some examples of which are toweling, milk and juice cartons, paper bags, and liner board for corrugated containers.
As stated in Handbook for Pulp and Paper Technologists, Gary A. Smook, Angus Wilde Publications, 1992 (which is incorporated herein by reference): "Paper has traditionally been defined as a felted sheet formed on a fine screen from a water suspension of fibers. Current paper products generally conform to this definition except that most products also contain non-fibrous additives. Dry forming methods are now utilized for the manufacture of a few specialty paper products. Pulp is the fibrous raw material for papermaking. Pulp fibers are usually of vegetable origin, but animal, mineral, or synthetic fibers may be used for special applications. The distinction between paper and paperboard is based on product thickness. Nominally, all sheets above 0.3 mm thickness are classed as paperboard; but enough exceptions are applied to make the distinction somewhat hazy."
Because of increased commercial emphasis on developing paper products based on recovered or recycled cellulose, there is growing interest in developing paper which is readily repulpable. Paper and paperboard waste materials are difficult to repulp in aqueous systems without special chemical treatment when they contain wet strength resins.
Improving the repulpability of paper containing wet strength resins has generally been achieved by modifying the repulping conditions. However, many conventional repulping processes used for wet strength paper result in the formation of environmentally undesirable chlorine-containing degradation products, involve strong oxidizing agents, or proceed slowly.
There is a need for improved methods for making paper products that will be readily repulpable without significantly lowering the wet and dry strength properties of the paper.
BRIEF SUMMARY OF THE INVENTION
The present invention relates to repulpable paper products comprising: papermaking fibers; cationic strength additives; and sulfopolyester thermoplastic resins.
The present invention also relates to methods of improving the wet- strength of paper which comprises adding to the paper during the papermaking process cationic strength additives; and sulfopolyester thermoplastic resins.
The present invention relates to paper products comprising: papermaking fibers; cationic strength additives; and sulfopolyester thermoplastic resins.
The present invention relates to methods of improving the wet-strength of cellulosic paper comprising adding to the papermaking fibers during the papermaking process cationic strength additives and sulfopolyester thermoplastic resins. DETAILED DESCRIPTION
The present invention may be understood more readily by reference to the following detailed description of the invention and to the Examples included therein.
Before the present compositions of matter and methods are disclosed and described, it is to be understood that this invention is not limited to specific synthetic methods or to particular formulations, unless otherwise indicated, and, as such, may vary from the disclosure. It is also to be understood that the terminology used is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention.
The singular forms "a", "an", and the "the" include plural referents, unless the context clearly dictates otherwise.
Optional or optionally means that the subsequently described events or circumstances may or may not occur. The description includes instances where the events or circumstances occur, and instances where they do not occur.
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." Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range. 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.
Throughout this application, where patents or publications are referenced, the disclosures of these references in their entireties are intended to be incorporated by reference into this application, in order to more fully describe the state of the art to which the invention pertains.
Some relevant technical terms as used in the context of the present invention are meant to be understood as follows (unless specifically indicated otherwise throughout the description). "Papermaking fibers," as used herein, include all known cellulosic fibers or fiber mixes comprising cellulosic fibers. Fibers suitable for making the webs of this invention comprise any natural or synthetic cellulosic fibers including, but not limited to non-woody fibers, such as cotton or cotton derivatives, abaca, kenaf, sabai grass, flax, esparto grass, straw, jute hemp, bagasse, milkweed floss fibers, and pineapple leaf fibers; and woody fibers such as those obtained from deciduous and coniferous trees, including softwood fibers, such as northern and southern softwood kraft fibers; hardwood fibers, such as eucalyptus, maple, birch, and aspen. Woody fibers may be prepared in high-yield or low-yield forms and may be pulped in any known method, including kraft, sulfite, groundwood, thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), and bleached chemithermomechanical pulp (BCTMP), high-yield pulping methods and other known pulping methods. High brightness pulps, including chemically bleached pulps, may be used and unbleached or semi- bleached pulps may also be used. Recycled fibers are included within the scope of the present invention. Any known pulping and bleaching methods may be used. Fibers prepared from organosolv pulping methods may also be used. Suitable papermaking fibers may also include recycled fibers, virgin fibers, or mixes thereof.
Synthetic cellulose fibers are also suitable for use including rayon in all its varieties and other fibers derived from viscose or chemically modified cellulose. Chemically treated natural cellulosic fibers may be used such as mercerized pulps, chemically stiffened or crosslinked fibers, sulfonated fibers, and the like. Suitable synthetic polymeric fibers include rayon, polyolefin fibers, polyester fibers, polyamide fibers and the like. Suitable synthetic polymer fiber structures include monocomponent , bicomponent, and multi component fibers such as core-sheath, islands-in-the-sea, side-by-side, segmented pie, and the like.
In one embodiment of the present invention the papermaking fibers comprise woody fibers, softwood Kraft pulp, hardwood Kraft pulp, recycled fibers, non-woody fibers, synthetic polymeric fibers, glass fibers, or combinations thereof. In one embodiment the synthetic polymeric fibers have a mean fiber diameter of less than 5 microns. In another embodiment the synthetic polymeric fibers comprise greater than 50% of the total papermaking fiber or greater than 70% of the total papermaking fiber.
For good mechanical properties in using papermaking fibers, it may be desirable that the fibers be relatively undamaged and largely unrefined or only lightly refined. While recycled fibers may be used, virgin fibers are also useful for their mechanical properties and lack of contaminants. Mercerized fibers, regenerated cellulosic fibers, cellulose produced by microbes, rayon, and other cellulosic material or cellulosic derivatives may be used. Suitable papermaking fibers may also include recycled fibers, virgin fibers, or mixes thereof.
As used herein, "high yield Pulp fibers" are those papermaking fibers of pulps produced by pulping processes providing a yield of about 65 percent or greater. Yield is the resulting amount of processed fiber expressed as a percentage of the initial wood mass. High yield pulps include bleached chemithermomechanical pulp (BCTMP), chemithermomechanical pulp (CTMP) pressure/pressure thermomechanical pulp (PTMP), thermomechanical pulp (TMP), thermomechanical chemical pulp (TMCP), high yield sulfite pulps, and high yield Kraft pulps, all of which contain fibers having high levels of lignin. Characteristic high-yield fibers can have lignin content by mass of about 1 percent or greater. Suitable high yield pulp fibers, after being prepared by pulping and optional bleaching steps and prior to being formed into dry bales or webs, in one embodiment can also be characterized by being comprised of comparatively whole, relatively undamaged fibers, high freeness (250 Canadian Standard Freeness (CSF) or greater, and low fines content (less than 25 percent by the Britt jar test). In one embodiment, the high-yield fibers are predominately softwood, for example northern softwood.
As used herein, the term "cellulosic" is meant to include any material having cellulose as a major constituent, and specifically comprising about 50 percent or more by weight of cellulose or cellulose derivatives. Thus, the term includes cotton, typical wood pulps, non-woody cellulosic fibers, cellulose acetate, cellulose triacetate, rayon, viscose fibers, thermomechanical wood pulp, chemical wood pulp, debonded chemical wood pulp, lyocell and other fibers formed from solutions of cellulose in NMMO, milkweed, or bacterial cellulose. Fibers that have not been spun or regenerated from solution may be used exclusively, if desired, or at least about 80% of the web may be free of spun fibers or fibers generated from a cellulose solution.
One aspect of the present invention relates to the production of paper products including paper and paper board from an aqueous slurry of papermaking fibers. It was discovered that the paper products of the present invention containing a cationic strength additive and a sulfopolyester thermoplastic resin resulted in paper products with improved or maintained wet strength and dry strength and with significantly enhanced repulpability.
One embodiment of the present invention relates to repulpable paper product comprising: papermaking fibers; cationic strength additives; and thermoplastic sulfopolyester resins.
Another embodiment of the present invention relates to paper product comprising: papermaking fibers; cationic strength additives; and thermoplastic sulfopolyester resins. The paper products according the present invention provide enhance repulpability.
In addition to enhanced repulability the paper products according to the present invention also provide enhanced sheet strength, increased machine speed, and improved retention. The present invention also allows the papermakers to simplify the wet end by reducing or eliminating the use of certain wet end additives, including dry strength resins, cationic starches, drainage and retention aids, and coagulants. When the present invention is used as both a wet and dry strength aid, the absorbency of the paper product is not decreased. The present invention provides the following improvements in sheet performance: lower basis weight, increased recycle fiber utilization, the ability to provide dispersion at higher concentration or in solid form, extended shelf life, reduced Kraft utilization, immediate cure, improved print receptivity, improved surface strength, improved sheet processibility, improved machine runnability, increased production, higher sheet ash content and filler cost savings, improved fiber recovery, reduced Whitewater solids and turbidity, increased retention of wet strength additive, reduced system deposition, provides high levels of controllable drainage, improved formation, increased machine speed, reduced dryer energy consumption, simplified and cleaner wet end resulting from fewer additives, cost-effective additive scheme, and wet end chemical efficiency gains.
It is common to include various inorganic and organic materials to the aqueous slurry of pulp or papermaking fibers for improving the paper products and the papermaking process. The process of making the paper products according to the present invention can be carried out on any conventional paper making apparatus.
In general, the process of the present invention includes providing a slurry of papermaking fibers, adding the components of the present invention to the slurry of pulp papermaking fibers, depositing the slurry of pulp papermaking fibers containing the components of the present invention on a forming fabric, and drying the slurry to form a paper web.
hi one embodiment of the present invention, the fibrous web to be formed from the papermaking fibers treated in accordance with the present invention may be wet-laid, such as webs may be formed with known papermaking techniques wherein the dilute aqueous fiber slurry is disposed on a moving wire to filter out the fibers and form a paper web which is subsequently dewatered by combinations of units including suction boxes, wet presses, dryer units, and the like. Capillary dewatering may also be applied to remove water from the web.
Any conventional drying method or dryers may be used according to the present invention. Drying operations may include drum drying, through drying, steam drying such as superheated steam drying, displacement dewatering, Yankee drying, infrared drying, microwave drying, radio frequency drying in general, and impulse drying.
A moist fibrous web may also be formed by foam forming processes, wherein the treated fibers are entrained or suspended in a foam prior to dewatering, or wherein foam is applied to a paper web prior to dewatering or drying.
The fibrous web is generally a random plurality of papermaking fibers that can, optionally, be joined together with a binder. Any papermaking fibers, as herein defined, or mixtures thereof may be used, such as bleached fibers from a kraft or sulfite chemical pulping process. Recycled fibers may also be used, as may cotton linters or papermaking fibers comprising cotton. Both high- yield and low-yield fibers may be used. In one embodiment, the fibers may be predominantly hardwood, such as at least 50% hardwood or about 60% hardwood or greater or about 80% hardwood or greater or substantially 100% hardwood. In another embodiment, the web is predominantly softwood, such as at least about 50% softwood or at least about 80% softwood, or about 100% softwood. In another embodiment, the web is predominantly synthetic polymeric fiber, such as at least about 50% synthetic polymeric fiber or at least about 80% synthetic polymeric fiber, or about 100% synthetic polymeric fiber.
The fibrous web of the present invention may be formed from a single layer or multiple layers. Stratified webs may also be formed wherein at least one layer comprises softwood fibers while another layer comprises hardwood or other fiber types. Layered structures produced by any means known in the art are within the scope of the present invention. In the case of multiple layers, the layers are generally positioned in a juxtaposed or surface-to-surface relationship and all or a portion of the layers may be bound to adjacent layers. The paper web may also be formed from a plurality of separate paper webs wherein the separate paper webs may be formed from single or multiple layers.
One embodiment of the present invention provides a method of improving the wet-strength of a cellulosic paper which comprises adding to the paper during the papermaking process a cationic strength additive; and a sulfopolyester thermoplastic resin.
The process for manufacturing paper products or the repulpable paper products according to the present invention comprises a number of steps. One step comprises forming an aqueous slurry of papermaking fibers or pulp or which can be performed by conventional means, i.e., known mechanical, chemical and semi-chemical, etc., pulping processes. Another step comprises adding to the aqueous slurry of papermaking fibers or pulp cationic strength additives and thermoplastic sulfopolyester resins. This can be done at any point, before sheet formation or it can also be applied after sheet formation from a tub size or at a size press or from showers to the dried or partially dried sheet. Yet another step comprises sheeting and drying the aqueous slurry of papermaking or pulp fibers containing the cationic thermosetting resin. This can be done by any conventional means.
In one embodiment, the components of the present invention comprising the cationic strength additives and the thermoplastic sulfopolyester resins are added to the pulp slurry separately, though depending on desired strength characteristics of the web, either the cationic strength additives or the thermoplastic sulfopolyester resins may be added to the slurry before the other.
During the papermaking process, the cationic strength additive can be incorporated by various methods including addition in the pulp fiber slurry or incorporation at the pulp press. In one embodiment of the present invention, the cationic strength additives are added to the slurry before the sulfopolyester thermoplastic resin. Without being bound by any theory, the cationic strength additive bonds to the anionically charged cellulose pulp fibers which results in a positively charged pulp fiber. Subsequently, the anionically charged sulfopolyester thermoplastic resin is applied to pulp fiber which results in an ionic bond. The sulfopolyester resin can be applied by various methods including spray application.
In another embodiment, the process of the present invention includes providing a slurry of pulp or papermaking fibers, sequentially adding the components of the present invention to the aqueous slurry of pulp or papermaking fibers, depositing the slurry of pulp or papermaking fibers containing the components of the present invention on a forming fabric, and drying the slurry to form a paper web. Such components may also be sprayed, printed, or coated onto the web after formation, while wet, or added to the wet end of the papermaking machine prior to formation. According to the present invention, the components comprising the cationic strength additives and the thermoplastic sulfopolyester resins may be added to the slurry in a ratio from about a 1 :5 to about a 5:1, as desired.
The pH of the slurry may be adjusted during the process. For example, the pH of the slurry may be adjusted to an acidic pH, such as about 6 or less in one embodiment. In another embodiment, however, the pH may be adjusted to greater than about 6. When the desired viscosity is reached, sufficient water is then added to adjust the solids content of the resin solution to about 15% or less, the product cooled to about 25° C. and then stabilized by adding sufficient acid to reduce the pH at least to about 6 and preferably to about 5. Any suitable acid such as hydrochloric, sulfuric, nitric, formic, phosphoric and acetic acid may be used to stabilize the product.
The paper web of the present invention may have any conventional bulk weight. In one embodiment, the paper web of the present invention may have a bulk greater than about 2 cc/g. For example, the paper web may have a bulk greater than about 5 cc/g. The dry tensile index of the paper web may be any conventional value. For example, the dry tensile index of the paper web can be greater than about 20 Nm/g in one embodiment. In another embodiment, the dry tensile index of the paper web can be greater than about 22 Nm/g. In yet another embodiment, the dry tensile index can be greater than about 25 Nm/g. In general, the basis weight of the paper webs of the present invention can be any desired basis weight. For instance, in one embodiment, the paper web may have a basis weight between about 5 and about 200 gsm.
Other conventional chemical additives that can be used in the papermaking process according to the present invention are: rosin size, reactive size (alkenyl succinic anhydride or alkyl ketene dimer), surface size, starch, retention aids, drainage aids, formation aids, flocculants, creping aids (adhesives and release agents), dry strength resins (cationic starch, guar gums, polyacrylamides), defoamers, scavengers for anionic trash and stickies control, fillers (clay, calcium carbonate, titanium dioxide), optical brightening aids and dyes.
Cationic strength additives
During papermaking and wet laid nonwovens hydraulic manufacturing processes, chemical additives are often incorporated to improve the wet strength and/or dry strength of paper and paperboard products. These chemical additives are commonly known as wet and dry strength additives and are available from a number of commercially available sources.
Examples of permanent wet strength additives include polyamide epichlorohydrin and polyamidoamine epichlorohydrin and are collectively known as PAE resins. Examples of wet strength additives are based on chemistries such as polyacrylamide and glyoxalated polyacrylamide (GPAM) resins.
According to the present invention, the cationic strength additives may consist of either wet strength or dry strength additives and include glyoxylated polyacrylamides, polyacrylamides, polyamide epichlorohydrins (PAEs), starches and other cationic additives well known to those skilled in the art. Polyamide epichlorohydrin, polyamidoamine epichlorohydrin and polyamine epichlorohydrin resins and are collectively known as PAE resins. PAE resins are widely used in the papermaking industry due to their ability to impart a high degree of wet strength to numerous paper products, including tissue, towel, wipes and corrugated board. PAE resins do not improve the dry strength of paper or paperboard and products containing these resins are generally considered not to be repulpable. Paper products containing wet strength additives, although generally repulpable; often have insufficient wet strength for many applications. Upon complete wetting, paper products derived from wet strength additives typically degrade within minutes to hours.
Suitable cationic strength additives used in accordance with the present invention include PAE resins, glyoxylated polyacrylamide resins, starches, polyacrylamides, and other wet strength and dry strength additives commonly known to those skilled in the art.
Procedures for making PAE resins are well known in the literature and are described in more detail in U.S. Pat. No. 3,772,076, which is incorporated herein by reference. PAE resins are sold by Ashland, Inc., Wilmington, Delaware, under the trade name Kymene® and by Georgia Pacific, Inc., Atlanta, Georgia, under the trade name Amres®. A typical procedure for synthesizing a PAE resin is as follows. A polyalkylene polyamine is reacted with an aliphatic dicarboxylic acid to form a polyamidoamine backbone. An example of a polyamidoamine is the reaction product of diethyl enetriamine with an adipic acid or ester of a dicarboxylic acid derivative. The resulting polyamidoamine is then reacted with epichlorohydrin in aqueous solution. The resulting product is diluted and neutralized with a strong mineral acid to a pH below 3.0.
Acrylamide polymers modified with glyoxal are known as glyoxalated polyacrylamide resins. Procedures for synthesizing glyoxylated polyacrylamide are well known in the literature and are described in more detail in U.S. Pat No.
3,556,932, which is incorporated herein by reference. Glyoxylated polyacrylamide resins are sold by Kemira, Inc., Kennesaw, Georgia, under the trade name Parez®. The acrylamide polymer may contain monomers to modify ionic properties. The acrylamide base polymer is reacted with sufficient glyoxal under aqueous alkaline conditions until a slight increase in viscosity occurs. The resulting product is then quenched with acid. Approximately half of the added glyoxyal remains unreacted and dissolved in the water. It is also possible to pre-blend the acrylamide polymer and glyoxal in a dry particulate state and subsequently add this blend to warm water to form a glyoxalated polyacrylamide resin. Dry strength additives include materials such as starches that may be cationic, quaternary or nonionic in nature. Examples of dry strength additives suitable for use in the present invention include cationic derivatives of polysaccharides (such as starch, guar, cellulose, and chitin); polyamine; polyethyleneimine; vinylalcohol-vinylamine copolymers; cationic acrylic homo- and copolymers such as polyacrylamide, polydiallyldimethylammonium chloride and copolymers of acrylic acid, acrylic esters and acrylamide with diallyldimethylammonium chloride, acryloyloxyethyltrimethylammoniurn chloride, methacryloyloxyethyltrimethylammonium methylsulfate, methacryloyloxyethyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride.
Other cationic strength resins that may be used in the present invention are: aminopolyamide-epi resins (e.g. Kymene® 557H-resin); polyamine-epi resins (e.g. Kymene® 736 resin), epoxide resins (e.g. Kymene® 450 and Kymene® 2064 resins); polyethylenimine, ureaformaldehyde resins; melamine- formaldehyde resins; glyoxalated polyacrylamides (e.g. Hercobond® 1000 resin, Parez 63 INC); polyisocyanates; and reactive starches (oxidized starch, dialdehyde starch, blocked reactive group starch).
The amount of cationic strength additive is generally from about 0.25 to about 3.00 weight % on a dry basis, based on the weight of the dried paper. For example in some embodiments of the present invention the amount of cationic strength additive is from about 0.25-3.00 weight percent, 0.25-2.00 weight percent, or 0.25-1.50 weight percent. In other embodiments, the cationic strength additive may be about 2 weight % on a dry basis, based on the weight of the dried paper, or about 1 weight %, or about 0.5 weight %. In one embodiment of the present invention similar amounts of wet strength additive and sulfopolyester are used.
Sulfopolyester thermoplastic resins
The sulfopolyesters of the present invention comprisedicarboxylic 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 sulfopolyeseter 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 sulfopolyeseter 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 25. degree. C. 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-norbomanedicarboxylic; 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- 1 ,4-cyclohexane-dicarboxylate 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, hi 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 "-SO.sub.3M" wherein M is the cation of the sulfonate salt. The cation of the sulfonate salt may be a metal ion such as Li.sup.+, Na.sup.+, K.sup.+, Mg.sup.++, Ca.sup.++, Ni.sup.++, Fe.sup.++, 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. Pat. 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 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 0.4 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 sulfopolyesters 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. Pat. Nos. 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 diols include ethylene glycol; diethylene glycol; triethylene glycol; polyethylene glycols; 1,3-propanediol; 2,4-dimethyl-2-ethylhexane-l,3- diol; 2,2-dimethyl-l,3-propanediol; 2-ethyl-2-butyl-l,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-- (OCH.sub.2— CH.sub.2).sub.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 diethyl ene 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 CARBOWAX.RTM., a product of Dow Chemical Company (formerly Union Carbide). Typically, PEG's 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 sulfopolyesters of the present invention has a glass transition temperature, abbreviated herein as "Tg", of at least 25. degree. C. as measured on the dry polymer using standard techniques, such as differentical 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 200.degree. C. 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 30.degree. C, at least 35.degree. C, at least 40. degree. C, at least 5O.degree. C, at least 60. degree. C, at least 65. degree. C, at least 80. degree. C, and at least 9O.degree. C. Although other Tg's are possible, typical glass transition temperatures of the dry sulfopolyesters our invention are about 30.degree. C, about 48. degree. C, about 55. degree. C, about 65.degree. C, about 7O.degree. C, about 75.degree. C, about 85. degree. C, and about 9O.degree. C.
Our invention also provides sulfopolyesters which comprise: (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-- (OCH.sub.2-- CH.sub.2).sub.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.
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 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 present 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. Pat. Nos. 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 15O.degree. C. to about 25O.degree. 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"). Preferably, the temperature for the ester interchange reaction ranges from about 180.degree. C. to about 230.degree. 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). 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 23O.degree. C. to about 350.degree. C, preferably about 250.degree. C. to about 310.degree. C. and most preferably about 26O.degree. C. to about 29O.degree. 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. Pat. 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 180.degree. C. to about 280. degree. C, more preferably ranging from about 22O.degree. C. to about 27O.degree. C. This low molecular weight polymer may then be polymerized by a polycondensation reaction.
The amount of thermoplastic sulfopolyester resin is generally from about 0.25 to about 3.00 weight % on a dry basis, based on the weight of the dried paper. For example in one embodiment the amount of sulfopolyester is from about 0.25-3.00 weight percent, 0.25-2.00 weight percent, or 0.25-1.50 weight percent . In another embodiment the amount of thermoplastic sulfopolyester can be about 0.05 weight % on a dry basis, or about 0.1 weight % or about 0.2 weight %. Typically the ratio of thermoplastic sulfopolyester resin to cationic strength additive is about 5:1 to about 1 :5. hi one embodiment the ratio of f sulfopolyester to cationic strength additive is about 1 :1.
The repulping process
The repulping process may be carried out using any conventional method. Typically, the process of repulping the paper to obtain recycled pulp fibers can be carried out by any mechanical action that disperses dry pulp fibers into an aqueous pulp fiber suspension. Conditions for repulping, as well as equipment commercially used, are discussed in "Handbook for Pulp & Paper Technologists, Second Edition" by G. A. Smook, Angus Wilde Publications, 1992, pp 194-195 and 211-212, which reference is incorporated herein by reference in its entirety.
It was found that paper prepared by the process of the present invention can be repulped in substantially less time than is required to repulp the same paper at about the same level of wet-strength.
The paper products of the present invention are suitable for use in the following areas: paper towels; napkins; facial tissue; liquid packaging board (milk carton, juice carton); poultry boxes; produce boxes; caπϊerboard; butchers wrap; bleached bag; poster board; table cloth; wallboard tape; currency paper; map paper; tea bag; corrugating medium; paper plates; molded products (egg cartons); laminating grades; flooring felt; coffee filter; bread wrap; multiwall bag; shingle wrap, etc.
The recycled pulp fibers prepared by the repulping process of the present invention can be used to make paper by conventional paper making processes, which comprise providing an aqueous suspension of the recycled pulp fibers and then sheeting and drying the aqueous suspension to obtain paper. The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
This invention can be further illustrated by the following examples of potential embodiments thereof, although it will be understood that these examples are included merely for the purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated. Parts and percentages mean parts by weight and percentages by weight, unless otherwise specified.
EXAMPLES
The examples were conducted using EastONE S85030 sulfopolyester dispersion to determine the effect of its addition on wet strength, dry strength and repulpability of paper in comparison to commercially available additives such as Kymene® and Hercobond® products from Hercules Incorporated, Wilmington, DE.
Preparation of sulfopolyester and polyamide epichlorohydrin (PAE) solutions:
A 3 wt% solution of a sulfopolyester was prepared as follows. 500 grams of distilled water was placed into a beaker heated to approximately 88.degrees.C on a hot plate. 15.5 grams of sulfopolyester pellets were added and continually stirred while maintaining a temperature of 88.degrees.C F for 10-15 minutes or until all of the sulfopolyester had dissolved. The mixture was cooled and distilled water was added to achieve a total solution weight of 515.5 grams.
A 3 wt% solution of a PAE solution was prepared as follows. 500 grams of distilled water was placed into a beaker. 160 grams of a 12.5 wt% solution of a commercially available PAE solution was added to the beaker and stirred. Coating procedure:
Each of the 3 wt% solutions was diluted, respectively, using distilled water such that when 3 ml of the solution was applied to the paper sheet, the target add-on concentration of 0.5 wt% was achieved.
3 drops of food coloring were added to each of the solutions as a visual aid to ensure uniform coverage of the solutions on the paper. An 8 1A" x 11" sheet of Lydall paper was placed on top of a larger piece of release paper. Lydall 18- l/2# Manning 514 saturating paper sheets weighing 1.87 ± 0.01 grams were used. The release paper was parchment paper laminated to aluminum foil.
A control was prepared as follows. 5 ml of distilled water was added to the paper sheet using a 5 ml volumetric pipette. The water was gently rolled into the sheet using a 2 inch rubber hand roller. The paper sheet, with the release sheet attached, was dried for 5 minutes in a 93.degree.C convection oven. The dried sheet was stored for 4 days under a 2 pound flat weight. This sample is referred to as the Control.
A sample containing 0.5 wt% PAE resin was prepared as follows. 5 ml of distilled water was added to the paper sheet using a 5 ml volumetric pipette. The water was gently rolled into the sheet using a hand roller. 3 ml of the diluted PAE solution was added with a 3 ml syringe to the pre-wetted paper. The solution was gently rolled into the sheet using a hand roller until uniform color was achieved. The paper sheet, with the release sheet attached, was dried for 5 minutes in a 93.degree.C convection oven. The dried sheet was stored for
4 days under a 2 pound flat weight. This sample is referred to as Sample 1. A sample containing 0.5 wt% sulfopolyester resin was prepared as follows.
5 ml of distilled water was added to the paper sheet using a 5 ml volumetric pipette. The water was gently rolled into the sheet using a hand roller. 3 ml of the diluted sulfopolyester solution was added with a 3 ml syringe to the pre- wetted paper. The solution was gently rolled into the sheet using a hand roller until uniform color was achieved. The paper sheet, with the release sheet attached, was dried for 5 minutes in a 93.degree.C convection oven. The dried sheet was stored for 4 days under a 2 pound flat weight. This sample is referred to as Sample 2.
An example of the present invention containing 0.25 wt% PAE and 0.25 wt% sulfopolyester was prepared as follows. 5 ml of distilled water was added to the paper sheet using a 5 ml volumetric pipette. The water was gently rolled into the sheet using a hand roller. 3 ml of the diluted PAE solution was added with a 3 ml syringe to the pre-wetted paper. The solution was gently rolled into the sheet using a hand roller until uniform color was achieved. The sheet was allowed to sit for 2 minutes. 3 ml of the diluted sulfopolyester solution was subsequently added to the paper with a 3 ml syringe. The sulfopolyester solution was gently hand rolled into the paper. The paper sheet, with the release sheet attached, was dried for 5 minutes in a 93.degree.C convection oven. The dried sheet was stored for 4 days under a 2 pound flat weight. This sample is referred to as Sample 3. The control and Samples 1 , 2 and 3 were evaluated for dry strength and wet strength using the following TAPPI test methods:
• T494-om-88: Tensile Breaking Properties of Paper and Paperboard (Using Constant Rate of Elongation Apparatus)
• T456-om-87: Tensile Breaking Strength of Water-Saturated Paper and Paperboard ("Wet Tensile Strength")
The repulpability of the paper samples was determined as follows. A brass hydropulper manufactured by Hermann Manufacturing Company was used for testing. The hydropulper was a 2 liter vessel with a 3000 rpm, 3A horsepower tri-rotor. The hydropulper had a diameter of 6 inches and a height of 10 inches.
Samples were cut into two 1 inch squares. A 2 liter sample of water was maintained at 2O.degrees.C and poured into the hydropulper. The counter was set to zero and both samples were placed into the hydropulper. The samples were pulped at intervals of 500 revolutions. After each of the 500 revolutions, the hydropulper was temporarily stopped and a fluorescent inspection light was held over the basin to determine whether or not the samples had been fully pulped. The number of sets per 500 revolutions was recorded. After 15,000 revolutions, samples were considered not repulpable and testing was discontinued. The test results are shown below in Table 1.
Table 1. Test results for control, Sam le 1 , Sam le and Sam le 3.
Figure imgf000030_0001
* Note: After 15,000 revolutions, the sample was considered not repulpable and testing was discontinued.

Claims

THAT WHICH IS CLAIMED IS:
1. A repulpable paper product comprising: papermaking fibers; a cationic strength additive; and a thermoplastic sulfopolyester resin.
2. The repulpable paper products of claim 1 wherein the sulfopolyester resin 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 sulfonate groups attached to an aromatic or cycloaliphatic ring wherein said 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 said functional groups are hydroxyl, carboxyl, or a combination thereof.
3. The repulpable paper products of claim 2 wherein the dicarboxylic acids are selected from aliphatic diacids, cycloaliphatic dicarboxylic acids, aromatic dicarboxylic acids, and combinations thereof.
4. The repulpable paper products of claim 3 wherein the dicarboxylic acids are selected from succinic, glutaric, adipic, azelaic, sebacic, fumaric, maleic, itaconic, 1,3-cyclohexane dicarboxylic, 1 ,4-cyclohexanedicarboxylic, diglycolic, 2,5-norbornanedicarboxylic, phthalic, terephthallc, 1,4- naphthalenedlcarboxylic, 2,5-naphthalenedicarboxylic, 2,6- naphthalenedicarboxylic, 2,7-naphthalenedicarboxylic, diphenic, 4,4'- oxydibenzoic, 4,4'-sulfonyldibenzoic, isophthalic, and combinations thereof.
5. The repulpable paper products of claim 2 wherein the sulfomonomer is a metal sulfonate salt of a sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalic acid, or combinations thereof.
6. The repulpable paper products of claim 2 wherein the diol residues are selected from ethylene glycol, diethylene glycol, triethylene glycol, poly(ethylene) glycols, 1 ,3-propanediol, 2,4-dimethyl-2-ethylhexane-l,3- diol, 2,2-dimethyl-l,3-propanediol, 2-ethyl-2-butyl-l,3-propanediol, 2- ethyl-2-isobutyl-l,3-propanediol, 1,3-butanedlol, 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, and combinations thereof.
7. The repulpable paper products of claim 2 wherein the branching monomer is
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.
8. The repulpable paper products of claim 1 wherein the cationic strength additive is selected from polyacrylamide resins, polyamide epihalohydrin resins polyamine epihalohydrin resins, polyamidoamine epichalohydrin resins, polyalkyleneimine resins, urea-formaldehyde resins, melamine- formaldehyde resins, cationic polysaccharides or combinations thereof.
9. The repulpable paper products of claim 8 wherein the cationic strength additive is selected from cationic glyoxylated polyacrylamide resins or polyamidoamine epichlorohydrin resins.
10. The repulpable paper products according to claim 1 wherein the papermaking fibers are selected from woody fibers, softwood fibers, hardwood fibers, non-woody fibers, synthetic polymeric fibers, recycled fibers, glass fibers, or combinations thereof.
11. The repulpable paper products according to claim 10 wherein the synthetic polymeric fibers are greater than 50% of the total papermaking fiber.
12. The repulpable paper products according to claim 1 1 wherein said synthetic polymeric fibers have a mean fiber diameter of less than 5 microns.
13. The repulpable paper products of claim 1 wherein the amount of cationic strength additive is about 0.25 weight % to about 3 weight % on a dry basis and the amount of thermoplastic sulfopolyester resin is about 0.25 to about
3.00 weight %, on a dry basis relative to the weight of papermaking fiber.
14. The repulpable paper products of claim 1 wherein the ratio of thermoplastic sulfopolyester resin to cationic strength additive is about 5:1 to about 1 :5.
15. The repulpable paper products of claim 1 wherein the ratio of sulfopolyester to cationic strength additive is about 1 : 1
16. A method of improving the wet-strength of cellulosic paper comprising adding to the papermaking fibers during the papermaking process a cationic strength additive; and a sulfopolyester thermoplastic resin.
17. The method of claim 16 wherein the cationic strength additive and sulfopolyester thermoplastic resin are added to an aqueous slurry of papermaking fibers during the papermaking process.
18. The method of claim 16 wherein said cationic strength additive is added to an aqueous slurry of papermaking fibers and the sulfopolyester thermoplastic resin is applied onto a paper web resulting from the dewatering of said papermaking fibers.
19. The method of claim 18 wherein the thermoplastic sulfopolyester resin is applied to the paper web by spray application.
20. The method of claim 16 wherein the resulting paper products exhibit enhanced repulpability.
21. A paper product comprising: papermaking fibers consisting of one or more of woody fibers, softwood fibers, hardwood fibers, non-woody fibers, synthetic polymeric fibers, recycled fibers, or glass fibers;
cationic strength additives consisting of one or more of polyacrylamide resins, polyamide epihalohydrin resins polyamine epihalohydrin resins, polyamidoamine epichalohydrin resins, polyalkyleneimine resins, urea- formaldehyde resins, melamine-formaldehyde resins, or cationic polysaccharides; and
thermoplastic sulfopolyester resins 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 said 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-0H 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 said functional groups are hydroxyl, carboxyl, or a combination thereof.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100269995A1 (en) * 2009-04-24 2010-10-28 Eastman Chemical Company Sulfopolyesters for paper strength and process
US9587328B2 (en) 2011-09-21 2017-03-07 Donaldson Company, Inc. Fine fibers made from polymer crosslinked with resinous aldehyde composition
US10300415B2 (en) 2013-03-09 2019-05-28 Donaldson Company, Inc. Fine fibers made from reactive additives

Families Citing this family (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7892993B2 (en) 2003-06-19 2011-02-22 Eastman Chemical Company Water-dispersible and multicomponent fibers from sulfopolyesters
US20120175074A1 (en) * 2010-10-21 2012-07-12 Eastman Chemical Company Nonwoven article with ribbon fibers
US20120183861A1 (en) 2010-10-21 2012-07-19 Eastman Chemical Company Sulfopolyester binders
US9435056B2 (en) 2011-09-21 2016-09-06 Donaldson Company, Inc. Fibers made from soluble polymers
CN103132383B (en) * 2011-11-25 2017-04-12 纳尔科公司 Sizing agent pretreatment for improving paper strength accessory ingredient performance in papermaking
US8906200B2 (en) 2012-01-31 2014-12-09 Eastman Chemical Company Processes to produce short cut microfibers
US9303357B2 (en) 2013-04-19 2016-04-05 Eastman Chemical Company Paper and nonwoven articles comprising synthetic microfiber binders
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
CN103882771B (en) * 2014-02-25 2016-01-13 南通玖伍捌科技企业孵化器有限公司 A kind of paper making auxiliary agent composition and preparation method thereof
JP6385084B2 (en) * 2014-03-11 2018-09-05 スリーエム イノベイティブ プロパティズ カンパニー Filter, manufacturing method thereof, and filtration system
FI20180084A1 (en) 2018-07-13 2020-01-14 Paptic Oy Water-dispersible composite structure and method of producing the same
US11286619B2 (en) 2018-08-23 2022-03-29 Eastman Chemical Company Bale of virgin cellulose and cellulose ester
US11441267B2 (en) 2018-08-23 2022-09-13 Eastman Chemical Company Refining to a desirable freeness
US11299854B2 (en) 2018-08-23 2022-04-12 Eastman Chemical Company Paper product articles
US11339537B2 (en) 2018-08-23 2022-05-24 Eastman Chemical Company Paper bag
US11639579B2 (en) 2018-08-23 2023-05-02 Eastman Chemical Company Recycle pulp comprising cellulose acetate
US11401659B2 (en) 2018-08-23 2022-08-02 Eastman Chemical Company Process to produce a paper article comprising cellulose fibers and a staple fiber
US11332885B2 (en) 2018-08-23 2022-05-17 Eastman Chemical Company Water removal between wire and wet press of a paper mill process
US11414818B2 (en) 2018-08-23 2022-08-16 Eastman Chemical Company Dewatering in paper making process
US11390991B2 (en) 2018-08-23 2022-07-19 Eastman Chemical Company Addition of cellulose esters to a paper mill without substantial modifications
US11512433B2 (en) 2018-08-23 2022-11-29 Eastman Chemical Company Composition of matter feed to a head box
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US4233196A (en) * 1979-04-30 1980-11-11 Eastman Kodak Company Polyester and polyesteramide compositions
US20040209058A1 (en) * 2002-10-02 2004-10-21 Chou Hung Liang Paper products including surface treated thermally bondable fibers and methods of making the same
US20070196401A1 (en) * 2004-02-19 2007-08-23 Yoshihiro Naruse Nano-Fiber Compound Solutions, Emulsions And Gels, Production Method Thereof, Nano-Fiber Synthetic Papers, And Production Method Thereof
US20080311815A1 (en) * 2003-06-19 2008-12-18 Eastman Chemical Company Nonwovens produced from multicomponent fibers

Family Cites Families (638)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
NL246230A (en) 1958-12-09
US3075952A (en) 1959-01-21 1963-01-29 Eastman Kodak Co Solid phase process for linear superpolyesters
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
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
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
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
US4210685A (en) * 1978-05-22 1980-07-01 Basf Wyandotte Corporation Polyester-starch sized paper, sizing composition, and process therefor
US4288503A (en) 1978-06-16 1981-09-08 Amerace Corporation Laminated microporous article
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
US4304901A (en) 1980-04-28 1981-12-08 Eastman Kodak Company Water dissipatable polyesters
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
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
US4996252A (en) 1988-07-28 1991-02-26 Eastman Kodak Company Ink composition containing a blend of a polyester and an acrylic polymer
US5039339A (en) 1988-07-28 1991-08-13 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
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
US4910292A (en) 1988-10-14 1990-03-20 Eastman Kodak Company Water-dissipatable polyester resins and coatings prepared therefrom
US4863785A (en) 1988-11-18 1989-09-05 The James River Corporation Nonwoven continuously-bonded trilaminate
US5281306A (en) 1988-11-30 1994-01-25 Kao Corporation Water-disintegrable cleaning sheet
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
JP2703971B2 (en) 1989-01-27 1998-01-26 チッソ株式会社 Ultrafine composite fiber and its woven or nonwoven fabric
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
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
FR2682956B1 (en) 1991-10-29 1994-01-07 Rhone Poulenc Chimie PROCESS FOR THE PREPARATION OF WATER-SOLUBLE AND / OR HYDRODISPERSABLE POLYESTERS AND USE OF SUCH POLYESTERS FOR SIZING TEXTILE THREADS.
US5503907A (en) 1993-07-19 1996-04-02 Fiberweb North America, Inc. Barrier fabrics which incorporate multicomponent fiber support webs
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
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
US5292581A (en) 1992-12-15 1994-03-08 The Dexter Corporation Wet wipe
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
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
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
US5674479A (en) 1993-06-25 1997-10-07 Eastman Chemical Company Clear aerosol hair spray formulations containing a linear sulfopolyester in a hydroalcoholic liquid vehicle
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
ATE174389T1 (en) 1993-10-15 1998-12-15 Kuraray Co WATER-SOLUBLE, HOT-FELTED BINDING FIBERS MADE OF POLYVINYL ALCOHOL, NON-WOVEN MATERIALS CONTAINING THESE FIBERS AND METHOD FOR PRODUCING SUCH FIBER AND THIS NON-WOVEN MATERIAL
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
CA2128483C (en) 1993-12-16 2006-12-12 Richard Swee-Chye Yeo Flushable compositions
KR970700743A (en) 1993-12-29 1997-02-12 해리 제이. 그윈넬 WATER-DISPERSIBLE ADHESIVE COMPOSITION AND PROCESS
US5543488A (en) 1994-07-29 1996-08-06 Eastman Chemical Company 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
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
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
US6229002B1 (en) 1995-06-07 2001-05-08 Nexstar Pharmaceuticlas, Inc. Platelet derived growth factor (PDGF) nucleic acid ligand complexes
US5759926A (en) 1995-06-07 1998-06-02 Kimberly-Clark Worldwide, Inc. Fine denier fibers and fabrics made therefrom
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
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
US5916678A (en) 1995-06-30 1999-06-29 Kimberly-Clark Worldwide, Inc. Water-degradable multicomponent fibers and nonwovens
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
JPH10110398A (en) * 1996-10-02 1998-04-28 Futaba Fine Chem Kk Sizing agent
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
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
US5935880A (en) 1997-03-31 1999-08-10 Wang; Kenneth Y. Dispersible nonwoven fabric and method of making same
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
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
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
US6348679B1 (en) 1998-03-17 2002-02-19 Ameritherm, Inc. RF active compositions for use in adhesion, bonding and coating
AU3091399A (en) 1998-03-17 1999-10-11 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
US6211309B1 (en) 1998-06-29 2001-04-03 Basf Corporation Water-dispersable materials
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
AU6509399A (en) 1998-10-06 2000-04-26 Fiber Innovation Technology, Inc. Splittable multicomponent elastomeric fibers
US6838402B2 (en) 1999-09-21 2005-01-04 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
US6592218B1 (en) * 1999-03-10 2003-07-15 Seydel Research, Inc. Ink jet recording method
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
US6441267B1 (en) 1999-04-05 2002-08-27 Fiber Innovation Technology Heat bondable biodegradable fiber
US6509092B1 (en) 1999-04-05 2003-01-21 Fiber Innovation Technology Heat bondable biodegradable fibers with enhanced adhesion
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
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 & VOSE COMPANY Filter media
US6171685B1 (en) 1999-11-26 2001-01-09 Eastman Chemical Company Water-dispersible films and fibers based on sulfopolyesters
US6177193B1 (en) 1999-11-30 2001-01-23 Kimberly-Clark Worldwide, Inc. Biodegradable hydrophilic binder fibers
US6576716B1 (en) 1999-12-01 2003-06-10 Rhodia, Inc Process for making sulfonated polyester compounds
DE60030162T2 (en) 1999-12-01 2007-08-09 Rhodia Inc. PROCESS FOR PREPARING SULFONATED POLYESTERS
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
US6428900B1 (en) 2000-03-09 2002-08-06 Ato Findley, Inc. Sulfonated copolyester based water-dispersible hot melt adhesive
DE10013315C2 (en) 2000-03-17 2002-06-06 Freudenberg Carl Kg Pleated filter from a multi-layer filter medium
US6316592B1 (en) 2000-05-04 2001-11-13 General Electric Company Method for isolating polymer resin from solution slurries
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
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
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
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
US20050208286A1 (en) 2000-09-21 2005-09-22 Hartmann Mark H Polymeric composites having enhanced reversible thermal properties and methods of forming thereof
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
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
US6361784B1 (en) 2000-09-29 2002-03-26 The Procter & Gamble Company Soft, flexible disposable wipe with embossing
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
US6838403B2 (en) 2000-12-28 2005-01-04 Kimberly-Clark Worldwide, Inc. Breathable, biodegradable/compostable laminates
ES2378982T3 (en) 2000-12-28 2012-04-19 Danisco A/S Separation procedure
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
US6381817B1 (en) 2001-03-23 2002-05-07 Polymer Group, Inc. Composite nonwoven fabric
EP1243675A1 (en) 2001-03-23 2002-09-25 Nan Ya Plastics Corp. Microfiber and its manufacturing method
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
US6743506B2 (en) 2001-05-10 2004-06-01 The Procter & Gamble Company High elongation splittable multicomponent fibers comprising starch and polymers
US20030077444A1 (en) 2001-05-10 2003-04-24 The Procter & Gamble Company Multicomponent fibers comprising starch and polymers
US20020168912A1 (en) 2001-05-10 2002-11-14 Bond Eric Bryan Multicomponent fibers comprising starch and biodegradable 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
WO2004001375A2 (en) 2002-06-21 2003-12-31 Burntside Partners Inc Multi-functional product markers and methods for making and using the same
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
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
KR101029515B1 (en) 2002-08-05 2011-04-18 도레이 카부시키가이샤 Porous fiber
US20050026527A1 (en) 2002-08-05 2005-02-03 Schmidt Richard John Nonwoven containing acoustical insulation laminate
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
JP4208517B2 (en) 2002-08-07 2009-01-14 富士フイルム株式会社 Polymer solution concentration method and apparatus
CN1293260C (en) 2002-08-07 2007-01-03 东丽株式会社 Artificial suede-type leather and process for producing the same
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
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
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
US20040127127A1 (en) 2002-12-30 2004-07-01 Dana Eagles Bicomponent monofilament
US6989194B2 (en) 2002-12-30 2006-01-24 E. I. Du Pont De Nemours And Company Flame retardant fabric
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
US7687143B2 (en) 2003-06-19 2010-03-30 Eastman Chemical Company Water-dispersible and multicomponent fibers from sulfopolyesters
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
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
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
JP4252442B2 (en) * 2003-12-26 2009-04-08 花王株式会社 Paper quality improver
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
US7285504B2 (en) 2004-04-23 2007-10-23 Air Products Polymers, L.P. Wet tensile strength of nonwoven webs
US7195819B2 (en) 2004-04-23 2007-03-27 Invista North America S.A.R.L. Bicomponent fiber and yarn comprising same
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
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
EP1781850A2 (en) 2004-07-16 2007-05-09 Reliance Industries Limited Self-crimping fully drawn high bulk yarns and method of producing thereof
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
US7291270B2 (en) 2004-10-28 2007-11-06 Eastman Chemical Company Process for removal of impurities from an oxidizer purge stream
US7094466B2 (en) 2004-10-28 2006-08-22 E. I. Du Pont De Nemours And Company 3GT/4GT biocomponent fiber and preparation thereof
US7390760B1 (en) 2004-11-02 2008-06-24 Kimberly-Clark Worldwide, Inc. Composite nanofiber materials and methods for making same
ES2541469T3 (en) 2004-11-05 2015-07-20 Donaldson Company, Inc. Spray separator
CA2525315C (en) 2004-11-05 2010-02-23 Sara Lee Corporation Molded non-woven fabrics and methods of molding
PL3138621T3 (en) 2004-11-05 2020-06-29 Donaldson Company, Inc. Filter medium and structure
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
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
KR101298892B1 (en) 2005-09-30 2013-08-21 가부시키가이샤 구라레 Leather-like sheet and method of manufacturing the same
US20070074628A1 (en) 2005-09-30 2007-04-05 Jones David C Coalescing filtration medium and process
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
CA2642186A1 (en) 2006-02-13 2007-08-23 Donaldson Company, Inc. Filter web comprising fine fiber and reactive, adsorptive or absorptive particulate
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
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
MX2008012228A (en) 2006-03-31 2008-10-02 Procter & Gamble Nonwoven fibrous structure comprising synthetic fibers and hydrophilizing agent.
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
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
US20080003905A1 (en) 2006-06-30 2008-01-03 Canbelin Industrial Co., Ltd. Mat
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
US7803275B2 (en) 2006-07-14 2010-09-28 Exxonmobil Research And Engineering Company Membrane separation process using mixed vapor-liquid feed
US7858163B2 (en) 2006-07-31 2010-12-28 3M Innovative Properties Company Molded monocomponent monolayer respirator with bimodal monolayer monocomponent media
US7902096B2 (en) 2006-07-31 2011-03-08 3M Innovative Properties Company Monocomponent monolayer meltblown web and meltblowing apparatus
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
US20080160859A1 (en) 2007-01-03 2008-07-03 Rakesh Kumar Gupta Nonwovens fabrics produced from multicomponent fibers comprising sulfopolyesters
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
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
US20110171890A1 (en) 2008-08-08 2011-07-14 Kuraray Co., Ltd. Polishing pad and method for manufacturing the polishing pad
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
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
US8512519B2 (en) * 2009-04-24 2013-08-20 Eastman Chemical Company Sulfopolyesters for paper strength and process
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
RU2414950C1 (en) 2009-07-09 2011-03-27 Федеральное государственное унитарное предприятие "Научно-исследовательский физико-химический институт им. Л.Я. Карпова" Filtration material
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
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
EP2292309A1 (en) 2009-08-07 2011-03-09 Ahlstrom Corporation Nanofibers with improved chemical and physical stability and web containing nanofibers
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
KR20120079842A (en) 2009-10-21 2012-07-13 쓰리엠 이노베이티브 프로퍼티즈 캄파니 Porous multilayer articles and methods of making
AU2010308287B2 (en) 2009-10-21 2013-09-19 3M Innovative Properties Company Porous supported 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 (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US4233196A (en) * 1979-04-30 1980-11-11 Eastman Kodak Company Polyester and polyesteramide compositions
US20040209058A1 (en) * 2002-10-02 2004-10-21 Chou Hung Liang Paper products including surface treated thermally bondable fibers and methods of making the same
US20080311815A1 (en) * 2003-06-19 2008-12-18 Eastman Chemical Company Nonwovens produced from multicomponent fibers
US20070196401A1 (en) * 2004-02-19 2007-08-23 Yoshihiro Naruse Nano-Fiber Compound Solutions, Emulsions And Gels, Production Method Thereof, Nano-Fiber Synthetic Papers, And Production Method Thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100269995A1 (en) * 2009-04-24 2010-10-28 Eastman Chemical Company Sulfopolyesters for paper strength and process
US8512519B2 (en) * 2009-04-24 2013-08-20 Eastman Chemical Company Sulfopolyesters for paper strength and process
US9587328B2 (en) 2011-09-21 2017-03-07 Donaldson Company, Inc. Fine fibers made from polymer crosslinked with resinous aldehyde composition
US10300415B2 (en) 2013-03-09 2019-05-28 Donaldson Company, Inc. Fine fibers made from reactive additives

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