EP3067445A1 - Procédé pour biofonctionnalisation de matériaux textiles - Google Patents

Procédé pour biofonctionnalisation de matériaux textiles Download PDF

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Publication number
EP3067445A1
EP3067445A1 EP15195767.7A EP15195767A EP3067445A1 EP 3067445 A1 EP3067445 A1 EP 3067445A1 EP 15195767 A EP15195767 A EP 15195767A EP 3067445 A1 EP3067445 A1 EP 3067445A1
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EP
European Patent Office
Prior art keywords
weight
polymer
temperature
extruder
copper silicate
Prior art date
Legal status (The legal status 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 status listed.)
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Application number
EP15195767.7A
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German (de)
English (en)
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EP3067445B1 (fr
Inventor
Jadwiga SÓJKA-LEDAKOWICZ
Jerzy Chrusciel
Marcin Kudzin
Magdalena Kiwala
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Instytut Wlokiennictwa
Inst Wlokiennictwa
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Instytut Wlokiennictwa
Inst Wlokiennictwa
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Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/08Melt spinning methods
    • D01D5/098Melt spinning methods with simultaneous stretching
    • D01D5/0985Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • D01F1/103Agents inhibiting growth of microorganisms
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D01F6/625Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters

Definitions

  • the present invention relates to a method for biofunctionalization of textile materials which leads to obtaining antibacterial and antifungal properties.
  • the structure of the coatings was examined by X-ray diffraction (XRD) method and by UV-Vis spectroscopy and HIRBS.
  • the obtained coatings showed high antibacterial activity against Escherichia coli strains which was increasing together with the increase of metal concentration, and decreasing with the increase of heat treatment temperature during the process of forming Cu nanoparticles.
  • the most effective antimicrobial properties were exhibited by the coatings which were not thermally treated under an oxidizing or reducing atmosphere.
  • SiO 2 nanoparticles served as a substrate for the continuous deposition of copper.
  • the chemical structure and morphology of the nanocomposite was examined by the X-ray photoelectron spectroscopy (XPS) method, scanning electron microscopy combined with energy-dispersive X-ray spectroscopy (SEM-EDX) and transmission electron microscopy (TEM).
  • XPS X-ray photoelectron spectroscopy
  • SEM-EDX energy-dispersive X-ray spectroscopy
  • TEM transmission electron microscopy
  • the copper nanoparticles homogeneously formed on the surface of SiO 2 nanoparticles did not undergo aggregation and exhibited excellent antibacterial activity with respect to multiple microorganisms.
  • AAS atomic absorption spectroscopy
  • Nanosilica which was modified on the surface with copper particles was used to remove the odor of mercaptans and sulfur compounds from petroleum. According to the publication in Langmuir, vol. 26, 15837-15844 (2010 ), silica modified by the addition of copper also exhibited antibacterial properties.
  • Copper silicate is used in medicine and biology, for instance, in controlled release of drugs and thermal treatment of tumors.
  • An additional advantage of copper silicate CuO ⁇ SiO 2 is the possibility to modify its surface and properties using hydrophobic substances, simple chemical processes and organofunctional compounds [ Bioelectrochemistry, vol. 87, 50-57 (2012 )].
  • the publication in the Nanoscale Research Letters journal, vol. 6, 594-602 (2011 ) reveals that cotton textiles impregnated with silica sol containing 0.5 - 2 % by weight of copper nanoparticles, having dried exhibited excellent antibacterial properties against both gram-negative and gram-positive bacteria.
  • the AMB Express magazine, vol. 3, 53 (2013 ) publishes an article describing very good antimicrobial properties of nanocomposites Cu ⁇ SiO 2 , obtained in the form of thin layers using the CVD method, against multiple hospital pathogens ( Acinetobacter baumannii, Klebsiella pneumoniae, Stenotrophomonas maltophilia, Enterococcus faecium, Staphylococcus aureus and Pseudomonas aeruginosa ).
  • the SEM method confirmed the nanostructure of Cu particles in the silica matrix.
  • the tested shells of nanocomposites Cu ⁇ SiO 2 can also be used for microbial protection of metal and ceramic surfaces.
  • the invention relates to a method for biofunctionalization of textile materials using copper silicate, preferably in the hydrate form, which is premixed with the polymer component and a plasticizer, then the whole is heated until polymer melts, and then the molten composition is subjected to pneumothermal extrusion and blowing the molten polymer in a stream of hot air.
  • Copper silicate hydrate is used in an amount of 0.1 - 4 % by weight.
  • polymers selected from the group consisting of polypropylene (PP) and its copolymers, polylactide (PLA), polyhydroxyalkanoate (PHA), polyethylene (PE) and / or mixtures thereof are used as polymer components.
  • a concentrate is used which comprises 1 - 25 % by weight of copper silicate hydrate with a selected polymer and mixed with the same or another polymer and the remaining ingredients in such weight proportions that the content of copper silicate hydrate in the manufactured fabric is 0.1 - 4 % by weight.
  • Plasticizers used are compounds having a liquid consistency selected from the group comprising: oligomers of ethylene glycol or propylene glycol, copolymers of ethylene glycol and propylene glycol, monoalkyl ethers of ethylene glycol oligomers, glycerin esters, citric acid esters or tartaric acid esters, pentaerythritol esters, dialkyl diesters of phthalic acid, paraffin oil, epoxy resin, hydroxyalkyl or hydroxy ether derivatives of polysiloxanes, oligoesters of silicic acid, oligo(dimethylsiloxanediol), polycarbonate diol, polycaprolactone, or polycaprolactone diol.
  • Plasticizers are used in an amount of 1.5 - 15 % by weight in relation to the mass of polymer or the mass of polymer mixture, preferably 2.5 - 5 % by weight.
  • an antioxidant 2,2'-Methylenebis(6-tert-butyl-4-methylphenol) (MBMTBP) or 2,2'-Methylenebis(6-tert-butyl-4-ethylphenol) (MBETBP) to the component system was applied.
  • MBMTBP 2,2'-Methylenebis(6-tert-butyl-4-methylphenol)
  • MBETBP 2,2'-Methylenebis(6-tert-butyl-4-ethylphenol
  • Example 1 (sample 5 in Table 1)
  • the equipment for manufacturing bioactive textile material comprises: screw extruder, a melt-blowing head, compressed air heater and the receiving device in the form of a moving drum.
  • PP processing parameters were as follows:
  • Example 2 (sample 2 in Table 1)
  • Example 3 (sample 3 in Table 1)
  • Example 4 (sample 10 in Table 1)
  • Example 5 (sample 13 in Table 1)
  • Example 6 (sample 25 in Table 2)
  • polycarbonate diol Desmophen C XP 2716 with an average molecular weight of 650 g/mol was added to 100.0 g of polylactide granulate (PLA) Ingeo 32510, followed by 0.5 % by weight of powdered copper silicate hydrate having the following chemical composition: 35.23 % by weight CuO, 62.16 % by weight SiO 2 , 18.52 % by weight H 2 O, 0.02 % by weight Na 2 O and 0.01 % by weight K 2 O.
  • PLA polylactide granulate
  • ethylene glycol oligomer with an average molecular weight of 600 g/mol (Polikol 600 - PEG) was added to 100.0 g of polylactide granulate (PLA) Ingeo 32510, followed by 0.5 % by weight of powdered copper silicate hydrate having the following chemical composition: 35.23 % by weight CuO, 62.16 % by weight SiO 2 , 18.52 % by weight H 2 O, 0.02 % by weight Na 2 O and 0.01 % by weight K 2 O.
  • Example 8 (sample 26 in Table 1)
  • ethylene glycol oligomer with an average molecular weight of 600 g/mol (Polikol 600 - PEG) was added to 100.0 g of polylactide granulate (PLA) Ingeo 32510, followed by 0.5 % by weight of powdered copper silicate hydrate having the following chemical composition: 35.23 % by weight CuO, 62.16 % by weight SiO 2 , 18.52 % by weight H 2 O, 0.02 % by weight Na 2 O and 0.01 % by weight K 2 O.
  • Example 9 (sample 20 in Table 1)
  • Example 10 (sample 7 in Table 1)
  • ethylene glycol oligomer with an average molecular weight of 600 g/mol (Polikol 600 - PEG) was added to 100.0 g of polypropylene granulate HL512 FB, followed by 4 % by weight of powdered copper silicate hydrate having the following chemical composition: 35.23 % by weight CuO, 62.16 % by weight SiO 2 , 18.52 % by weight H 2 O, 0.02 % by weight Na 2 O and 0.01 % by weight K 2 O.
  • Example 11 (sample 40 in Table 3)
  • ethylene glycol oligomer with an average molecular weight of 600 g/mol (Polikol 600 - PEG) was added to 100.0 g of polypropylene granulate HL512 FB (PP), followed by 1 % by weight of powdered copper silicate hydrate (having the following chemical composition: 35.23 % by weight CuO, 62.16 % by weight SiO 2 , 18.52 % by weight H 2 O, 0.02 % by weight Na 2 O and 0.01 % by weight K 2 O) as well as 0.15% by weight 2,2'-methylenebis (6-tert-butyl-4-methylphenol) (MBMTBP).
  • MBMTBP 2,2'-methylenebis (6-tert-butyl-4-methylphenol)
  • Example 12 (sample 41 in Table 3)
  • Example 13 (sample 42 in Table 3)
  • ethylene glycol oligomer with an average molecular weight of 600 g/mol (Polikol 600 - PEG) was added to 100.0 g of polypropylene granulate HL512 FB, followed by 1 % by weight of powdered copper silicate hydrate (having the following chemical composition: 35.23 % by weight CuO, 62.16 % by weight SiO 2 , 18.52 % by weight H 2 O, 0.02 % by weight Na 2 O and 0.01 % by weight K 2 O) as well as 0.25 % by weight 2,2'-methylenebis (6-tert-butyl-4-ethylphenol) (MBETBP).
  • MBETBP 2,2'-methylenebis (6-tert-butyl-4-ethylphenol)
  • Example 14 (sample 43 in Table 3)
  • Table 1 and Table 3 point to bactericidal and fungicidal properties of composite non-woven fabrics modified with copper silicate hydrate.
  • Table 1 Chemical compositions of composite non-woven fabrics (with PP or PLA) containing Polikol 600-PEG (or PCL-diol or other plasticizers), and hydrous copper silicate CuSiO 3 ⁇ xH 2 O and the results of their microbiological tests Sample No.
  • R -growth reduction factor for bacteria R L-growth reduction factor for bacteria L 1 -an addition of 0.15 phr of 2,2'-Methylenebis(6-tert-butyl-4-methylphenol)(MBMTBP)was used 2 -an addition of 0.20 phr of 2,2'-Methylenebis(6-tert-butyl-4-ethylphenol) (MBETBP) was used 3 - an addition of 0.25 phr of (MBMTBP) was used 4 - an addition of 0.20 phr of (MBETBP) was used
EP15195767.7A 2015-03-07 2015-11-23 Procédé pour biofonctionnalisation de matériaux textiles Active EP3067445B1 (fr)

Applications Claiming Priority (1)

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PL411473A PL231089B1 (pl) 2015-03-07 2015-03-07 Sposób biofunkcjonalizacji materiałów włókienniczych

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106757493A (zh) * 2017-01-13 2017-05-31 连云港杜钟新奥神氨纶有限公司 一种蓝色卫材氨纶制备方法
WO2022175771A1 (fr) 2021-02-18 2022-08-25 Lynam Pharma Limited Tissus non tissés biologiques et durables et leurs procédés de fabrication
EP4079946A1 (fr) * 2021-04-19 2022-10-26 Ergocom Company Limited Procédé de fabrication d'une étoffe non tissée pour masque obtenue par fusion-soufflage et masque utilisant cette étoffe

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08283013A (ja) * 1995-04-13 1996-10-29 Mizusawa Ind Chem Ltd 非晶質ケイ酸銅、その製法及びその用途
WO2004063088A1 (fr) * 2003-01-11 2004-07-29 Jtl Co., Ltd. Mousse a memoire de forme viscoelastique a effets antibacterien, deodorant et d'emission de rayons infrarouges lointains
EP1564316A1 (fr) * 2004-02-12 2005-08-17 Nisshinbo Industries, Inc. Article fibreux comprenant un plastique biodégradable
WO2009152349A1 (fr) * 2008-06-12 2009-12-17 3M Innovative Properties Company Fines fibres obtenues par fusion-soufflage et procédés de fabrication
US20120094120A1 (en) * 2010-10-18 2012-04-19 PurThread Technologies, Inc. Enhancing and preserving anti-microbial performance in fibers with pigments

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08283013A (ja) * 1995-04-13 1996-10-29 Mizusawa Ind Chem Ltd 非晶質ケイ酸銅、その製法及びその用途
WO2004063088A1 (fr) * 2003-01-11 2004-07-29 Jtl Co., Ltd. Mousse a memoire de forme viscoelastique a effets antibacterien, deodorant et d'emission de rayons infrarouges lointains
EP1564316A1 (fr) * 2004-02-12 2005-08-17 Nisshinbo Industries, Inc. Article fibreux comprenant un plastique biodégradable
WO2009152349A1 (fr) * 2008-06-12 2009-12-17 3M Innovative Properties Company Fines fibres obtenues par fusion-soufflage et procédés de fabrication
US20120094120A1 (en) * 2010-10-18 2012-04-19 PurThread Technologies, Inc. Enhancing and preserving anti-microbial performance in fibers with pigments

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* Cited by examiner, † Cited by third party
Title
ANTIMICROBIAL AGENTS AND CHEMOTHERAPY, vol. 51, 2007, pages 2605 - 2607
BIOCHIMICA ET BIOPHYSICA ACTA, vol. 1840, 2014, pages 3264 - 3276
BIOELECTROCHEMISTRY, vol. 87, 2012, pages 50 - 57
BIOMEDICAL MATERIALS, vol. 4, 2009, pages 045008
C.C. TRAPALIS ET AL., JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY, vol. 26, 2003, pages 1213 - 1218
COLLOIDS AND SURFACES B: BIOINTERFACES, vol. 108, 2013, pages 358 - 365
DIGEST JOURNAL OF NANOMATERIALS AND BIOSTRUCTURES, vol. 8, 2013, pages 869 - 876
DYES AND PIGMENTS, vol. 73, 2007, pages 298 - 304
FORMATEX, 2011, pages 197 - 209
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GABBAY, BORKOW ET AL., JOURNAL OF INDUSTRIAL TEXTILES, vol. 35, 2006, pages 323 - 335
INTERNATIONAL JOURNAL OF ANTIMICROBIAL AGENTS, vol. 33, 2009, pages 587 - 590
INTERNATIONAL JOURNAL OF PHARMACEUTICAL RESEARCH AND DEVELOPMENTS, vol. 6, 2014, pages 72 - 78
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY, 2014
JOURNAL OF BIOMEDICAL NANOTECHNOLOGY, vol. 8, 2012, pages 558 - 566
JOURNAL OF MATERIALS CHEMISTRY B, vol. 2, 2014, pages 846 - 858
JOURNAL OF MATERIALS SCIENCE, vol. 41, 2006, pages 5208 - 5212
LANGMUIR, vol. 26, 2010, pages 15837 - 15844
NANOSCALE RESEARCH LETTERS JOURNAL, vol. 6, 2011, pages 594 - 602
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THE AMB EXPRESS MAGAZINE, vol. 3, 2013, pages 53
THE JOURNAL OF PHYSICAL CHEMISTRY B, vol. 110, 2006, pages 24923 - 24928
THE OPEN BIOLOGY JOURNAL, vol. 6, 2013, pages 1 - 7

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106757493A (zh) * 2017-01-13 2017-05-31 连云港杜钟新奥神氨纶有限公司 一种蓝色卫材氨纶制备方法
WO2022175771A1 (fr) 2021-02-18 2022-08-25 Lynam Pharma Limited Tissus non tissés biologiques et durables et leurs procédés de fabrication
EP4079946A1 (fr) * 2021-04-19 2022-10-26 Ergocom Company Limited Procédé de fabrication d'une étoffe non tissée pour masque obtenue par fusion-soufflage et masque utilisant cette étoffe

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Publication number Publication date
PL411473A1 (pl) 2016-09-12
PL231089B1 (pl) 2019-01-31
EP3067445B1 (fr) 2017-10-04

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