EP3067445B1 - Procédé pour biofonctionnalisation de matériaux textiles - Google Patents

Procédé pour biofonctionnalisation de matériaux textiles Download PDF

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Publication number
EP3067445B1
EP3067445B1 EP15195767.7A EP15195767A EP3067445B1 EP 3067445 B1 EP3067445 B1 EP 3067445B1 EP 15195767 A EP15195767 A EP 15195767A EP 3067445 B1 EP3067445 B1 EP 3067445B1
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Prior art keywords
weight
polymer
temperature
extruder
copper silicate
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EP15195767.7A
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German (de)
English (en)
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EP3067445A1 (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

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • D01D5/0985—Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent 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
    • D01F6/46—Monocomponent 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent 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
    • D01F6/92—Monocomponent 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 in the hydrate form, which is premixed with the polymer component, a plasticizer and an antioxidant, then the whole is heated until the 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 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.
  • the antioxidants are used in the amount of 0.05 - 0.5 % by weight with respect to the mass of the polymer or the mass of polymer mixture, preferably 0.15 - 0.30 % by weight.
  • Example 1 (sample 5 in Table 1).
  • ethylene glycol oligomer with an average molecular weight of 600 g/mol (Polikol 600 - PEG) were added to 100.0 g of polypropylene granulate HL 512 FB (PP), followed by 2 % by weight of powdered anhydrous copper silicate.
  • 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).
  • ethylene glycol oligomer with an average molecular weight of 600 g/mol (Polikol 600 - PEG) were added to 100.0 g of polylactide granulate (PLA) Ingeo 32510, 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.
  • 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 were 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
  • Example 7 (sample 24 in Table 1).
  • ethylene glycol oligomer with an average molecular weight of 600 g/mol (Polikol 600 - PEG) were 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) were 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).
  • ethylene glycol oligomer with an average molecular weight of 600 g/mol (Polikol 600 - PEG) were added to 100.0 g of polylactide granulate (PLA) Ingeo 32510, followed by 0.1 % 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.
  • Example 10 (sample 7 in Table 1)
  • ethylene glycol oligomer with an average molecular weight of 600 g/mol (Polikol 600 - PEG) were 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) were 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).
  • ethylene glycol oligomer with an average molecular weight of 600 g/mol (Polikol 600 - PEG) were added to 100.0 g of polylactide granulate (PLA) Ingeo 32510, 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 0.20 % by weight 2,2'-methylenebis (6-tert-butyl-4-methylphenol) (MBMTBP).
  • PHA polylactide granulate
  • MBMTBP 2,2'-methylenebis (6-tert-butyl-4-methylphenol)
  • Example 13 (sample 42 in Table 3).
  • ethylene glycol oligomer with an average molecular weight of 600 g/mol (Polikol 600 - PEG) were 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).
  • ethylene glycol oligomer with an average molecular weight of 600 g/mol (Polikol 600 - PEG) were added to 100.0 g of polylactide granulate (PLA) Ingeo 32510, 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 0.30 % by weight 2,2'-methylenebis (6-tert-butyl-4-ethylphenol) (MBETBP).
  • PHA polylactide granulate
  • MBETBP 2,2'-methylenebis (6-tert-butyl-4-ethylphenol)
  • 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.

Claims (11)

  1. Le procédé de biofonctionnalisation de matériaux textiles par extrusion, où le composant polymère est pré-mélangé avec du silicate de cuivre et avec un plastifiant et un antioxydant, le tout est chauffé pour faire fondre le polymère, puis la composition fondue est soumise au processus de l'extrusion pneumothermique de l'alliage liquide de polymère dans un courant d'air chaud, caractérisé en ce que le silicate de cuivre est utilisé sous la forme d'un hydrate.
  2. Le procédé selon la revendication 1, caractérisé en ce quele silicate de cuivre contient 18,52 % en poids d'eau.
  3. Le procédé selon la revendication 1, caractérisé en ce quel'hydrate de silicate de cuivre est utilisé en une quantité de 0,1 à 4 % en poids.
  4. Le procédé selon la revendication 1, caractérisé en ce quele silicate de cuivre est utilisé sous la forme d'un concentré contenant de 1-25 % en poids d'hydrate de silicate de cuivre avec le polymère.
  5. Le procédé selon la revendication 1, caractérisé en ce qu'n tant que les composants du polymère sont utilisés des polymères choisis du groupe contenant du poloporpylène et ses copolymères, du polylactide, des polyhydroxyalcanoates, du polyéthylène et/ou leurs mélanges.
  6. Le procédé selon la revendication 1, caractérisé en ce queles plastifiants ont consistance liquide.
  7. Le procédé selon la revendication 1, caractérisé en ce qu'en tant que plastifiant sont utilisés les composés choisis du groupe contenant : les oligomères de l'éthylène ou de polypropylène glycol, les copolymères de l'éthylène glycol et du propylène glycol, les éthers monoalkyliques d'oligomères de l'éthylène glycol ; les esters de glycérine, les esters de l'acide citrique ou de l'acide tartrique, les esters de pentaérythritol, les esters dialkyliques de l'acide phtalique, l'huile de paraffine, la résine époxy, les oligoesters de l'acide silicique, les dérivés hydroxy éther de polysiloxanes, le policaprolactone, le polycaprolactonediol, ou le diol de polycarbonate
  8. Le procédé selon la revendication 1 ou 7, caractérisé en ce qu'en tant que plastifiant est utilisé un oligomère d'éthylène glycol.
  9. Le procédé selon la revendication 1, caractérisé en ce queles plastifiants sont utilisés en une quantité de 1,5-15 % en poids par rapport au au poids du polymère ou au poids du mélange de polymères, de préférence de 2,5 à 5% en poids.
  10. Le procédé selon la revendication 1, caractérisé en ce qu'en tant qu'antioxydant sont utilisés des dérivés de tert-butylphénol, de préférence 2,2' Méthylène-2,2'-bis(méthyl-4-tert-butyl-6-phénol ou 2,2'Méthylène-2,2'-bis(éthyl-4-tert-butyl-6-phénol).
  11. Le procédé selon la revendication 1 ou 10, caractérisé en ce queles antioxydants sont utilisés en une quantité de 0,05-0,5 % en poids par rapport au poids de polymère ou au poids du mélange de polymères, de préférence de 0,15 à 0,30 % en poids.
EP15195767.7A 2015-03-07 2015-11-23 Procédé pour biofonctionnalisation de matériaux textiles Active EP3067445B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PL411473A PL231089B1 (pl) 2015-03-07 2015-03-07 Sposób biofunkcjonalizacji materiałów włókienniczych

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EP3067445B1 true EP3067445B1 (fr) 2017-10-04

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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
EP4294974A1 (fr) 2021-02-18 2023-12-27 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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JP3519168B2 (ja) * 1995-04-13 2004-04-12 水澤化学工業株式会社 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
JP4512381B2 (ja) * 2004-02-12 2010-07-28 日清紡ホールディングス株式会社 生分解性プラスチックを含む繊維製品
EP3266909A1 (fr) * 2008-06-12 2018-01-10 3M Innovative Properties Co. 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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EP3067445A1 (fr) 2016-09-14
PL411473A1 (pl) 2016-09-12

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