US20060283567A1 - Cellulosed molded article having a functional effect and method for producing the same - Google Patents
Cellulosed molded article having a functional effect and method for producing the same Download PDFInfo
- Publication number
- US20060283567A1 US20060283567A1 US10/552,086 US55208605A US2006283567A1 US 20060283567 A1 US20060283567 A1 US 20060283567A1 US 55208605 A US55208605 A US 55208605A US 2006283567 A1 US2006283567 A1 US 2006283567A1
- Authority
- US
- United States
- Prior art keywords
- cellulosic
- fibres
- active
- fibers
- silver
- 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.)
- Abandoned
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 230000000694 effects Effects 0.000 title abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 51
- 150000002500 ions Chemical class 0.000 claims abstract description 31
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 23
- 239000013543 active substance Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims description 56
- 239000004332 silver Substances 0.000 claims description 56
- -1 silver ions Chemical class 0.000 claims description 27
- 239000003899 bactericide agent Substances 0.000 claims description 17
- 239000004753 textile Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 229920002678 cellulose Polymers 0.000 claims description 11
- 239000001913 cellulose Substances 0.000 claims description 11
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- 238000011067 equilibration Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 7
- 229920000058 polyacrylate Polymers 0.000 claims description 7
- 239000004971 Cross linker Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000742 Cotton Polymers 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- WAZPLXZGZWWXDQ-UHFFFAOYSA-N 4-methyl-4-oxidomorpholin-4-ium;hydrate Chemical compound O.C[N+]1([O-])CCOCC1 WAZPLXZGZWWXDQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims description 2
- 235000010199 sorbic acid Nutrition 0.000 claims description 2
- 239000004334 sorbic acid Substances 0.000 claims description 2
- 229940075582 sorbic acid Drugs 0.000 claims description 2
- 229920002994 synthetic fiber Polymers 0.000 claims description 2
- 210000002268 wool Anatomy 0.000 claims description 2
- 229940070721 polyacrylate Drugs 0.000 claims 4
- 229920000642 polymer Polymers 0.000 claims 4
- 239000002952 polymeric resin Substances 0.000 claims 3
- 229920003002 synthetic resin Polymers 0.000 claims 3
- 239000004745 nonwoven fabric Substances 0.000 claims 2
- 229920005594 polymer fiber Polymers 0.000 claims 2
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 claims 1
- 235000013580 sausages Nutrition 0.000 claims 1
- 239000012209 synthetic fiber Substances 0.000 claims 1
- 239000002759 woven fabric Substances 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 32
- 150000001768 cations Chemical class 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 9
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000845 anti-microbial effect Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000000813 microbial effect Effects 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 241000195493 Cryptophyta Species 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000011534 incubation Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 244000063299 Bacillus subtilis Species 0.000 description 3
- 235000014469 Bacillus subtilis Nutrition 0.000 description 3
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical class CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 241000427940 Fusarium solani Species 0.000 description 2
- 241000199919 Phaeophyceae Species 0.000 description 2
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000002241 glass-ceramic Substances 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229960002715 nicotine Drugs 0.000 description 2
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001225 therapeutic effect Effects 0.000 description 2
- 125000005208 trialkylammonium group Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 240000001929 Lactobacillus brevis Species 0.000 description 1
- 235000013957 Lactobacillus brevis Nutrition 0.000 description 1
- 241001584954 Lactobacillus brevis ATCC 14869 = DSM 20054 Species 0.000 description 1
- 235000003207 Lactobacillus brevis DSM 20054 Nutrition 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008275 binding mechanism Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940116441 divinylbenzene Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003641 microbiacidal effect Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic System; Titanates; Zirconates; Stannates; Plumbates
-
- 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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic System
- D06M11/42—Oxides or hydroxides of copper, silver or gold
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic System; Zincates; Cadmates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP 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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/20—Chemically or biochemically modified fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP 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
- D21H21/00—Non-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
- D21H21/14—Non-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
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2904—Staple length fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2904—Staple length fiber
- Y10T428/2905—Plural and with bonded intersections only
Definitions
- the invention relates to cellulosic forms as well as a method for producing cellulosic forms by the dry-wet extrusion process with improved and enhanced functional effects, especially applicable in medicine, hygiene, garment, paper manufacturing and packaging industry.
- the functional effect is directed to a steady and meticulously adjustable bactericide effect, especially for wound contact material, sports and leisure clothing, hospital textiles, filter and packaging papers.
- silver is for example galvanically deposited on the surface of polyamide silk.
- Working up of said galvanically silver-plated polyamide silk on knitters and moulders is problematical, since the silver layer of the polyamide silk is partially deposited on the yarn leading devices leading to numerous shut downs of said devices.
- metallic silver, silver-zeolite or silver-glass ceramics into the matrix of the fibre of melt spun fibres like polypropylene fibres, polyester fibres and polyamide fibres (Taschenbuch für die Textilindustrie 2003, Schiele & Schön Berlin, P. 124 ff).
- DE 10 140 772 discloses a method for producing cellulosic forms with incorporated algae. Said forms are able to adsorb metals from heavy metal containing media. The heavy metal loaded forms may be used as antibacterial and/or fungicidal material. The content of adsorbed heavy metals in said cellulosic forms is given as at least about 70 mg/kg, related to the total weight of the cellulosic forms.
- Patent Abstracts of Japan, Edition 0152, No. 01 (C-0834) of JP 3 054234 discloses the production of a cellulosic composition comprising an ion exchanger functionality, useful as binder for metal ions, wherein said production process consists of mixing a specifically generated cellulose and an anionic polymer followed by solidification of said mixture.
- Aim of the present invention is to provide a cellulosic form with functional effect as well as a method for preparing said cellulosic form, especially for the use in medicine, hygiene and garment, wherein said forms have a bactericide effect and wherein especially said advantages go along with breathable clothing.
- a further aim is to keep said active agents in a textile depot and further to obtain sufficient release of said agents from said depot over a period of time.
- the released concentrations of said agent should be controllable.
- the forms, especially fibres or foils, obtainable by the method of the invention should be formed thus, that they are useful for preparing wound overlays, band-aids, sanitary products, textiles, special papers and packaging material, because of the high adsorption ability of active agents.
- composites including differing fibres should be producible.
- the aim is reached in combination with the aforementioned discussed method according to the present invention by charging the cellulosic forms, wherein said forms are spun according to the dry-wet extrusion method and having incorporated weakly linked cationic active ion exchangers with active agents.
- the binding capacity for said active agents depends on the degree of cross-linking of the ion exchanger.
- the binding capacity for the cationic active agents like e.g. silver could be increased by more than the double amount, if polyacrylates are used, which were weakly cross-linked by a multifunctional cross-linker.
- Weakly cross-linked ion exchangers according to the present invention are ion exchangers with a decreased amount of cross-linkers.
- Usual ion exchanger resins show an amount of cross-linkers of 4 to 12 weight-%, based on the weight of the ion exchanger resin.
- Weakly cross-linked ion exchangers according to the present invention have an amount of cross-linkers ranging from 0.1 to 2.0 weight-%, preferably 0.3 to 1.5 weight-%, particularly preferably 0.5 to 1.2 weight-%.
- Fibres made with incorporated weakly cross-linked cation exchangers show a capacity for binding silver ions which surpasses the capacity of fibres with brown algae according to DE 10 140 772 up to the 28-fold.
- a fibre with 15 weight-% incorporated weakly cross-linked cationic ion exchanger may be loaded with about 80 g silver. Silver loads of fibres of >100 g Ag/kg fibre are possible, if the amount of the incorporated weakly cross-linked cation exchanger is increased accordingly.
- Said fibres may be mixed with other fibres, e.g. cotton, wool or synthetic fibres, to produce yarns with the desired silver content. This procedure allows the production of bactericidic yarns in a very economic way.
- ion exchangers are used on the basis of acrylic acid-divinylbenzene-copolymer-bound carboxyl groups or on the basis of a styrene-divinylbenzene-copolymer bound chelat forming imino-diacetic-acid as described in DE 19 917 614, fibres are obtained, which are comparable in their bactericide effect.
- the capacity for silver ions is less than 50% of the aforementioned weakly cross-linked cation exchangers.
- a measure for the bactericide effect of the fibres or yarns is the equilibration concentration of the active agent in aqueous solutions e.g. the concentration of the silver ions.
- fibres or yarns loaded with silver ions are put into distilled water at a temperature of 20° C., followed by a measurement of the equilibration concentration of the silver ions after 24 h.
- Table 1 shows the equilibration concentrations of silver ions and the load of silver in the fibres, while using weakly cross-linked cation exchangers or known ion exchangers cross-linked with divinyl-benzene.
- the equilibration concentration of silver ions is on a level which is above the necessary concentration of 0.01 to 1 mg/l to obtain a bactericide effect.
- the equilibration concentration may be controlled to each desired concentration level by mixing with other kinds of fibres.
- the fibres according to the present invention provide the equilibration concentration which is necessary to obtain an antimicrobial effect, at an increased Ag-content of the fibre at the same time.
- the advantages thereof are obvious.
- the equilibration concentration is uphold by the Ag deposited in the fibre. Due to the improved storing properties of the inventive fibres the equilibration concentration may be uphold over an extended period of time.
- fibres may be loaded with cation-active and anion-active bactericide ions, like silver ions and benzoic acid or asorbic acid.
- Such functionalised fibres with cation active agents within medical applications is possible.
- Such fibres may bind agents, like nicotine.
- Said fibres may be manufactured into band-aids and used for transdermal, therapeutic systems.
- Advantageously loading of said functional fibres may proceed by dipping the fibres into a solution of appropriate ions. Said dipping may be carried out continuously or in batch mode. When dipping in continuous mode it is preferred to load the cut fibre in a separate bath during subsequent treatment.
- Powdery weakly cross-linked cation exchanger based on a cross-linked copolymerisate of acrylic acid and sodium acrylate, having a grain size ⁇ 10 ⁇ m, is added to 12 weight-% cellulose solution in N-methylmorpholine-N-oxide monohydrate, in a weight proportion of 15 weight-%, based on the cellulose proportion.
- This spinning solution was homogenised in a kneader and spun with a spinning nozzle with 480 holes and a spinning hole diameter of 80 ⁇ m at a temperature of about 90° C. The draw off speed was about 30 m/min.
- the multifile fibre was led through several washing baths to wash out the residual N-methylmorpholine-N-oxides.
- the fibres were skidded and loaded in 10 L of 0.1 M silver nitrate solution per kg fibre. After loading the fibres were skidded and washed to remove residual silver nitrate. Finally the fibres are dried at a temperature of about 80° C. TABLE 2 yarn-count dtex 0.7 yarn-count related tensile tear resistance (dry) cN/tex 22.5 elongation (dry) % 14.8 yarn-count-related tear resistance of interwoven loops cN/tex 7.5 Silver content g/kg fiber 80
- Table 2 shows the parameters of the fibres as well as the silver content per fibre.
- a highly loaded fibre offers the advantage, that by blending this fibre with other textile fibres, e. g. cotton, silver loaded yarns can be economically obtained.
- the silver-fiber constitutes only a sixteenth of the yarn.
- Fibres are produced according to example 1 with a titre of 0.17 tex and a content of weakly cross-linked cation exchanger of 6 weight-%, based on the content of cellulose. These fibres are loaded with silver according to example 1. The fibre-parameters are given in table 3.
- Fibres are made according to Example 1 with a titre of 0.5 tex and a content of weakly cross-linked cation exchanger of 0.5 weight-%, based on the cellulosic content.
- the loading with silver ions is carried out according to Example 1.
- the parameters of the fibres are shown in table 3. Further, in table 3 a fibre without weakly cross-linked cation exchanger is shown for comparison.
- example 4 yarn-count dtex 0.5 0.5 yarn-count related tensile tear cN/tex 31.2 30.9 resistance (dry) elongation (dry) % 14.2 13.5 yarn-count-related tear cN/tex 9.1 8.5 resistance of loops silver content g/kg fiber 17.5 13.6
- Example 5 Working corresponding to Example 4 and adding to the slurry 6 weight-% of a weakly acid macroporous cation exchanger, based on cross-linked polyacrylate in its sodium-form, so that the spun fibre contains 6 weight-% ion exchanger based on the cellulose content, washing said fibre and loading it with silver ions according to Example 1, one obtains fibres with 13.6 g Ag/kg per fibre.
- Example 5 surprisingly shows that the ion exchanger on the basis of polyacrylate binds about half the amount of silver ions compared to the weakly cross-linked cation exchanger based on polyacrylates.
- the rise of the binding capacity of more than 100% leads to technical and economical advantages in that on one hand small amounts of the weakly cross-linked cation exchanger in the fibre barely influence the textile physical parameters, while on the other hand, based on the high incorporation of silver ions, an economical production by blending with other fibres is possible.
- Fibres with weakly cross-linked cation exchangers as well as common ion exchangers of the prior art, made according to Examples 1 to 5 are loaded with silver, copper (II) and zinc ions. The results are shown in Table 5.
- Table 5 metal content g/kg fiber fiber incorporated with copper silver silver/zinc 20 weight-% ion exchanger according to 23.7 57.1 23.9/27.5 example 4 (comparative example) 20 weight-% ion exchanger according to 11.5 41.7 36.4/24.5 example 5 (comparative example) 15 weight-% weakly linked cation 25.5 85.5 59.3/30.5 exchanger as in example 1 to 3
- Fibres loaded with copper ions, silver ions or a combination of silver ions and zinc ions may be used as bactericide fibres.
- the spinning solution is spun according to Example 1 with a titre of 0.5 tex.
- the fibres show a strength of 26.3 cN/tex, an elongation of 12.1% and a yarn-count related tear-resistance of loops of 8.6 cN/tex.
- the silver load is at 52.4 g silver/kg fibre and the load with benzoate at 16.6 g benzoate/kg fibre. These fibres possess a very strong bactericide effect.
- the example shows the appliccability of fibres according to the invention in combination with loaded fibres with anion exchangers and cation exchangers known from the prior art.
- Ion-exchanging fibres or foils according to the invention with incorporated cation exchangers, produced corresponding to example 2 are loaded with nicotine.
- the loaded fibres or foils are washed and dried.
- These fibres or foils can be processed into textile depots and can be applied as transdermal, therapeutic system.
- the bactericide properties of fibres, produced according to example 1, were determined following the European Pharmacopaeia (EP 2002), ‘Bioburden determination’.
- Papers were examined, which contain fibres according to example 1 in such an amount, that gradually altered silver contents in the paper of 190 mg Ag/kg paper, 760 mg Ag/kg paper and 3800 mg Ag/kg paper resulted.
- the examination was carried out with the following micro-organisms (Tables 6-9):
- the comparative sample was a paper without silver-containing fibres.
- the bacillus subtilis spores showed the highest resistance as expected. But also with these micro-organisms a decrease in microbial count could be achieved.
- Fibres produced according to example 1 were spun in combination with cotton to stocking-yarn with a titre of Nm 68/1 and a silver content of 1300 mg Ag/kg yarn. With this yarn a hose was knitted and examined on its bactericide effect (sample 31444083). The examination was carried out according to SN195924.
- the test-organism was lactobacillus brevis DSM 20054. As test sample a not anti-microbially equipped cotton fabric was used (Table 10). Five measurements were carried out on each sample as well as the test sample.
- the 24-hours-value of the growth-control (control, i. e. standard-fabric) has to be larger than the initial value by at least two orders of magnitude (AE ⁇ 2).
Abstract
Description
- The invention relates to cellulosic forms as well as a method for producing cellulosic forms by the dry-wet extrusion process with improved and enhanced functional effects, especially applicable in medicine, hygiene, garment, paper manufacturing and packaging industry.
- The functional effect is directed to a steady and meticulously adjustable bactericide effect, especially for wound contact material, sports and leisure clothing, hospital textiles, filter and packaging papers.
- It is well known that heavy metal ions like e.g. silver, quicksilver/mercury, copper, zinc and zirconium ions are deadening or growth inhibiting to bacteria, viruses, fungi or spores (Thurman et al., CRC Crit. Rev. In Environ. Contr. 18 (4), P. 295-315 (1989)). With respect to the bactericide effect silver ions are of particular interest. The important advantage of silver ions against other bactericide metal ions, like e.g. Hg2+, is the insensibility of the human metabolism against silver. The bactericide acting concentration is denoted for silver as 0.01-1 mg/l (Ullman's Encyclopedia of Industrial Chemistry (5. Edition), VCH 1993, Volume A 24, P. 160).
- This effect of silver ions is used in different applications. In the manufacture of textile fibres silver is for example galvanically deposited on the surface of polyamide silk. Working up of said galvanically silver-plated polyamide silk on knitters and moulders is problematical, since the silver layer of the polyamide silk is partially deposited on the yarn leading devices leading to numerous shut downs of said devices. It is further known to introduce metallic silver, silver-zeolite or silver-glass ceramics into the matrix of the fibre of melt spun fibres like polypropylene fibres, polyester fibres and polyamide fibres (Taschenbuch für die Textilindustrie 2003, Schiele & Schön Berlin, P. 124 ff).
- The use of silver-zeolite and silver-glass ceramics was also proposed for acrylic fibres. Also cellulosic fibres with bacteriostatic and bactericidal properties are available on the market. Incorporation of triclosan (2,4,4-trichloro(II)-hydroxyphenyleneether) into cellulosic fibres leads to a permanently bacteriostatic fibre (ITB International Textile Bulletin 3/2002). Said substance is active against bacteria usually occurring on skin, including pathogenic staphylococcus-types.
- DE 10 140 772 discloses a method for producing cellulosic forms with incorporated algae. Said forms are able to adsorb metals from heavy metal containing media. The heavy metal loaded forms may be used as antibacterial and/or fungicidal material. The content of adsorbed heavy metals in said cellulosic forms is given as at least about 70 mg/kg, related to the total weight of the cellulosic forms.
- It is further disclosed that by dipping a fibre with a content of brown algae of 11.39 weight-%, based on the weight of the fibre, into a 0.05 M AgNO3-solution a silver content of 1855 mg/kg per fibre was obtained. Since algae are natural products the capacity for binding said heavy metals varies. During binding of heavy metals onto algae different binding mechanisms are relevant, like ion exchange, complexing and further unknown reactions. The binding of said heavy metals onto said algae is therefore non-specific. A further disadvantage of said fibre is that only cations may be used for a bactericidal effect, but no bactericidal anions, e.g. benzoic acid and sorbic acid.
- WO 00/63470 relates to a method for the production of cellulosic forms with a high adsorption ability, wherein usual ion exchange particles with grain size of >=25 μm are added to said forms prepared by the Lyocell method. Furthermore, the adsorption of heavy metal ions is disclosed, namely of copper and lead, with a capacity of 0.01 mmol/g, using an anion exchanger of a styrene-divinyl benzene copolymer.
- Patent Abstracts of Japan, Edition 0152, No. 01 (C-0834) of JP 3 054234 discloses the production of a cellulosic composition comprising an ion exchanger functionality, useful as binder for metal ions, wherein said production process consists of mixing a specifically generated cellulose and an anionic polymer followed by solidification of said mixture.
- Aim of the present invention is to provide a cellulosic form with functional effect as well as a method for preparing said cellulosic form, especially for the use in medicine, hygiene and garment, wherein said forms have a bactericide effect and wherein especially said advantages go along with breathable clothing. A further aim is to keep said active agents in a textile depot and further to obtain sufficient release of said agents from said depot over a period of time. The released concentrations of said agent should be controllable. Further the forms, especially fibres or foils, obtainable by the method of the invention, should be formed thus, that they are useful for preparing wound overlays, band-aids, sanitary products, textiles, special papers and packaging material, because of the high adsorption ability of active agents. Finally composites including differing fibres should be producible.
- Further advantages are shown in the following description.
- The aim is reached in combination with the aforementioned discussed method according to the present invention by charging the cellulosic forms, wherein said forms are spun according to the dry-wet extrusion method and having incorporated weakly linked cationic active ion exchangers with active agents. Surprisingly it was found that the binding capacity for said active agents depends on the degree of cross-linking of the ion exchanger. Thus, the binding capacity for the cationic active agents, like e.g. silver could be increased by more than the double amount, if polyacrylates are used, which were weakly cross-linked by a multifunctional cross-linker.
- Weakly cross-linked ion exchangers according to the present invention are ion exchangers with a decreased amount of cross-linkers. Usual ion exchanger resins show an amount of cross-linkers of 4 to 12 weight-%, based on the weight of the ion exchanger resin. Weakly cross-linked ion exchangers according to the present invention have an amount of cross-linkers ranging from 0.1 to 2.0 weight-%, preferably 0.3 to 1.5 weight-%, particularly preferably 0.5 to 1.2 weight-%.
- Weakly cross-linked ion exchanger resins are characterized by the pronounced ability to swell considerably in aqueous solutions. Usual ion exchange resins with the aforementioned amount of cross-linkers show only a minor degree of swelling.
- Fibres made with incorporated weakly cross-linked cation exchangers show a capacity for binding silver ions which surpasses the capacity of fibres with brown algae according to DE 10 140 772 up to the 28-fold. Thus, the opportunity is given to produce fibres or foils which may be heavily loaded with cationic active bactericide agents like silver ions. A fibre with 15 weight-% incorporated weakly cross-linked cationic ion exchanger may be loaded with about 80 g silver. Silver loads of fibres of >100 g Ag/kg fibre are possible, if the amount of the incorporated weakly cross-linked cation exchanger is increased accordingly.
- Said fibres may be mixed with other fibres, e.g. cotton, wool or synthetic fibres, to produce yarns with the desired silver content. This procedure allows the production of bactericidic yarns in a very economic way.
- However, incorporation of ion exchangers leads with an increasing amount within the fibre to a disadvantageous influence on the textile physical parameters like strength, elongation and loop strength. In particular strength and loop strength will be reduced with an increasing amount of incorporated ion exchanger.
- Thus, it is also of economic interest to provide silver loaded fibres showing textile physical properties, like strength and loop strength which come close to the properties of fibres which do not contain incorporated ion exchangers.
- With the present invention it is possible to obtain fibres with a sufficient content of silver per fibre to show an adequate bactericide effect, but no disadvantages in view of the textile physical parameters. According to the present invention it is possible with 0.5 to 1.5 weight-%, based on the cellulose weight of the fibres, of incorporated weakly cross-linked cation exchanger to bind 5000 to 10.000 mg Ag/kg fibre. Such fibres have a sufficient bactericide effect in the known field of use and are equal to non-modified fibres concerning their textile physical parameters. Processing of such fibres and yarns made thereof is possible on all kind of textile machinery.
- If, instead of weakly cross-linked cation exchangers, ion exchangers are used on the basis of acrylic acid-divinylbenzene-copolymer-bound carboxyl groups or on the basis of a styrene-divinylbenzene-copolymer bound chelat forming imino-diacetic-acid as described in DE 19 917 614, fibres are obtained, which are comparable in their bactericide effect. However, the capacity for silver ions is less than 50% of the aforementioned weakly cross-linked cation exchangers.
- A measure for the bactericide effect of the fibres or yarns is the equilibration concentration of the active agent in aqueous solutions e.g. the concentration of the silver ions.
- For this purpose fibres or yarns loaded with silver ions are put into distilled water at a temperature of 20° C., followed by a measurement of the equilibration concentration of the silver ions after 24 h. Table 1 shows the equilibration concentrations of silver ions and the load of silver in the fibres, while using weakly cross-linked cation exchangers or known ion exchangers cross-linked with divinyl-benzene. As shown the equilibration concentration of silver ions is on a level which is above the necessary concentration of 0.01 to 1 mg/l to obtain a bactericide effect. The equilibration concentration may be controlled to each desired concentration level by mixing with other kinds of fibres.
TABLE 1 content of ion exchanger Ag-content of the fiber equilibration-concentration 7 weight % [g/kg] [mg/l Ag+] ion exchanger with 13.5 2.9 —COOH-groups ion exchanger with 17.5 3.6 chelating groups weakly linked cation 36.5 2.7 exchanger (inventive) - As shown in table 1, the fibres according to the present invention provide the equilibration concentration which is necessary to obtain an antimicrobial effect, at an increased Ag-content of the fibre at the same time. The advantages thereof are obvious.
- During the use of the fibres free Ag-ions are permanently released, whereby the equilibration concentration is uphold by the Ag deposited in the fibre. Due to the improved storing properties of the inventive fibres the equilibration concentration may be uphold over an extended period of time.
- If weakly cross-linked cation exchangers and strongly basic anion exchangers, based on styrene-divinylbenzene-copolymer with trialkylammonium-groups in chloride-form are incorporated into the fibre, said fibres may be loaded with cation-active and anion-active bactericide ions, like silver ions and benzoic acid or asorbic acid.
- Thus, it is possible to use silver ions together with anion active agents like e.g. benzoic acid and asorbic acid. Said substances are toxicologically unobjectable as shown in several publications and therefore they are qualified for a direct use in foods (Wallhäuβer, Sterilisation, Desinfektion, Konservierung, 4th edition, time 1988, P. 396). Processing of such fibres in paper manufacturing or foils made thereof provide antimicrobial packages for food.
- Further, the use of said functionalised fibres with cation active agents within medical applications is possible. Such fibres may bind agents, like nicotine. Said fibres may be manufactured into band-aids and used for transdermal, therapeutic systems.
- Advantageously loading of said functional fibres may proceed by dipping the fibres into a solution of appropriate ions. Said dipping may be carried out continuously or in batch mode. When dipping in continuous mode it is preferred to load the cut fibre in a separate bath during subsequent treatment.
- The invention and its properties will be illustrated more clearly by the following examples:
- Powdery weakly cross-linked cation exchanger, based on a cross-linked copolymerisate of acrylic acid and sodium acrylate, having a grain size<10 μm, is added to 12 weight-% cellulose solution in N-methylmorpholine-N-oxide monohydrate, in a weight proportion of 15 weight-%, based on the cellulose proportion. This spinning solution was homogenised in a kneader and spun with a spinning nozzle with 480 holes and a spinning hole diameter of 80 μm at a temperature of about 90° C. The draw off speed was about 30 m/min. The multifile fibre was led through several washing baths to wash out the residual N-methylmorpholine-N-oxides. The fibres were skidded and loaded in 10 L of 0.1 M silver nitrate solution per kg fibre. After loading the fibres were skidded and washed to remove residual silver nitrate. Finally the fibres are dried at a temperature of about 80° C.
TABLE 2 yarn-count dtex 0.7 yarn-count related tensile tear resistance (dry) cN/tex 22.5 elongation (dry) % 14.8 yarn-count-related tear resistance of interwoven loops cN/tex 7.5 Silver content g/kg fiber 80 - Table 2 shows the parameters of the fibres as well as the silver content per fibre. A highly loaded fibre offers the advantage, that by blending this fibre with other textile fibres, e. g. cotton, silver loaded yarns can be economically obtained. For a content of roughly 5000 mg Ag/kg yarn the silver-fiber constitutes only a sixteenth of the yarn.
- In contrast to the galvanised polyamide-fibres thus produced yarns show a good processability on knitting machines or moulders.
- Fibres are produced according to example 1 with a titre of 0.17 tex and a content of weakly cross-linked cation exchanger of 6 weight-%, based on the content of cellulose. These fibres are loaded with silver according to example 1. The fibre-parameters are given in table 3.
- Fibres are made according to Example 1 with a titre of 0.5 tex and a content of weakly cross-linked cation exchanger of 0.5 weight-%, based on the cellulosic content. The loading with silver ions is carried out according to Example 1. The parameters of the fibres are shown in table 3. Further, in table 3 a fibre without weakly cross-linked cation exchanger is shown for comparison.
TABLE 3 fiber without weakly linked cation example 2 example 3 exchanger yarn-count dtex 0.17 0.5 0.5 yarn-count related cN/tex 35.8 37.6 38.1 tensile tear resistance (dry) elongation (dry) % 13.0 11.4 11.8 yarn-count-related tear cN/tex 8.2 9.1 9.5 resistance of loops silver content g/kg fiber 36.6 4.6 — - It is evident from examples 1 to 3, that the silver content on a fibre is adjustable over a wide range via the content of weakly cross-linked cation exchanger. Even with 0.5 weight-% a high silver content is obtainable. The influence of 0.5 weight-% of the weakly cross-linked cation exchanger on the textile parameters of the fibre is marginal.
- To a cellulose slurry in 60% aqueous N-methylmorpholine-N-oxide an aqueous suspension of weakly acid macro-porous cation exchanger, based on styrene-divinylbenzene-copolymer with chelating groups of iminodiacetic acid, is added in such a concentration, that the spinned fibres reach a content of 6 weight-%, based on the cellulosic content. After spinning said fibres are washed and loaded with silver ions according to Example 1. Table 4 shows the parameters of the fibres.
TABLE 4 example 4 example 5 yarn-count dtex 0.5 0.5 yarn-count related tensile tear cN/tex 31.2 30.9 resistance (dry) elongation (dry) % 14.2 13.5 yarn-count-related tear cN/tex 9.1 8.5 resistance of loops silver content g/kg fiber 17.5 13.6 - Working corresponding to Example 4 and adding to the slurry 6 weight-% of a weakly acid macroporous cation exchanger, based on cross-linked polyacrylate in its sodium-form, so that the spun fibre contains 6 weight-% ion exchanger based on the cellulose content, washing said fibre and loading it with silver ions according to Example 1, one obtains fibres with 13.6 g Ag/kg per fibre. Example 5 surprisingly shows that the ion exchanger on the basis of polyacrylate binds about half the amount of silver ions compared to the weakly cross-linked cation exchanger based on polyacrylates. The rise of the binding capacity of more than 100% leads to technical and economical advantages in that on one hand small amounts of the weakly cross-linked cation exchanger in the fibre barely influence the textile physical parameters, while on the other hand, based on the high incorporation of silver ions, an economical production by blending with other fibres is possible.
- Fibres with weakly cross-linked cation exchangers as well as common ion exchangers of the prior art, made according to Examples 1 to 5 are loaded with silver, copper (II) and zinc ions. The results are shown in Table 5.
TABLE 5 metal content g/kg fiber fiber incorporated with copper silver silver/zinc 20 weight-% ion exchanger according to 23.7 57.1 23.9/27.5 example 4 (comparative example) 20 weight-% ion exchanger according to 11.5 41.7 36.4/24.5 example 5 (comparative example) 15 weight-% weakly linked cation 25.5 85.5 59.3/30.5 exchanger as in example 1 to 3 - Fibres loaded with copper ions, silver ions or a combination of silver ions and zinc ions may be used as bactericide fibres.
- A suspension of weakly cross-linked cation exchanger based on a cross-linked copolymerisate of acrylic acid and sodium acrylate and a strong basic anion exchanger, based on a styrene-divinylbenzene-copolymer with trialkylammonium-groups in chloride form, in 85% N-methylmorpholine-N-oxide is added in such an amount to a 11 weight-% cellulose solution in N-methylmorpholine-N-oxide-monohydrate, such that the spinning solution contains 11 weight-% cellulose, based on the cellulose content, 8 weight-% of the weakly cross-linked cation exchanger and 8 weight-% of said anion exchanger. After homogenisation the spinning solution is spun according to Example 1 with a titre of 0.5 tex. The fibres show a strength of 26.3 cN/tex, an elongation of 12.1% and a yarn-count related tear-resistance of loops of 8.6 cN/tex.
- The silver load is at 52.4 g silver/kg fibre and the load with benzoate at 16.6 g benzoate/kg fibre. These fibres possess a very strong bactericide effect. The example shows the appliccability of fibres according to the invention in combination with loaded fibres with anion exchangers and cation exchangers known from the prior art.
- Ion-exchanging fibres or foils according to the invention with incorporated cation exchangers, produced corresponding to example 2, are loaded with nicotine. The loaded fibres or foils are washed and dried. These fibres or foils can be processed into textile depots and can be applied as transdermal, therapeutic system.
- The bactericide properties of fibres, produced according to example 1, were determined following the European Pharmacopaeia (EP 2002), ‘Bioburden determination’.
- Papers were examined, which contain fibres according to example 1 in such an amount, that gradually altered silver contents in the paper of 190 mg Ag/kg paper, 760 mg Ag/kg paper and 3800 mg Ag/kg paper resulted. The examination was carried out with the following micro-organisms (Tables 6-9):
- Pseudomonas aeruginosa ATCC 9027
- Staphylococcus aureus ATCC 6538
- Bacillus subtilis spores ATCC 6633
- Fusarium solani spores ATCC 36031.
TABLE 6 Pseudomonas aeruginosa microbial count after respective incubation time silver content 0 minutes 1 day 3 days 7 days comparative 6.9 × 104 7.8 × 104 5.9 × 105 4.5 × 104 sample 190 mg Ag/kg 8.9 × 104 4.5 × 103 77 <10 760 mg Ag/kg 7.7 × 104 1.3 × 103 <10 <10 3800 mg Ag/kg 8.7 × 104 3.3 × 10 <10 <10 -
TABLE 7 Staphylococcus aureus microbial count after respective incubation time silver content 0 minutes 1 day 3 days 7 days comparative 1.1 × 105 1.2 × 105 1.4 × 105 9.6 × 104 sample 190 mg Ag/kg 1.3 × 105 1.1 × 105 4.6 × 103 36 760 mg Ag/kg 1.4 × 105 8.8 × 104 4.8 × 103 <10 3800 mg Ag/kg 1.2 × 105 4.9 × 104 1.1 × 103 <10 -
TABLE 8 Fusarium solani spores microbial count after respective incubation time silver content 0 minutes 1 day 3 days 7 days comparative 1.6 × 105 1.7 × 105 1.6 × 105 1.7 × 105 sample 190 mg Ag/kg 1.6 × 105 1.2 × 105 1.0 × 103 <10 760 mg Ag/kg 1.2 × 105 7.8 × 104 7.3 × 103 <10 3800 mg Ag/kg 1.6 × 105 8.8 × 104 1.4 × 103 <10 -
TABLE 9 Bacillus subtilis spores microbial count after respective incubation time silver content 0 minutes 1 day 3 days 7 days comparative 1.3 × 105 1.2 × 105 1.2 × 105 1.3 × 105 sample 190 mg Ag/kg 1.1 × 105 9.5 × 104 9.7 × 104 1.6 × 10 4 760 mg Ag/kg 1.2 × 105 1.1 × 105 8.4 × 104 1.7 × 10 4 3800 mg Ag/kg 1.3 × 105 8.8 × 104 7.7 × 104 1.1 × 10 4 - All results of the microbial count are afflicted with an error of measurement of 10%.
- The comparative sample was a paper without silver-containing fibres. For all micro-organisms a dependency of the microbicidal effect on duration of treatment and concentration of the silver-load could be found. The bacillus subtilis spores showed the highest resistance as expected. But also with these micro-organisms a decrease in microbial count could be achieved.
- Fibres produced according to example 1 were spun in combination with cotton to stocking-yarn with a titre of Nm 68/1 and a silver content of 1300 mg Ag/kg yarn. With this yarn a hose was knitted and examined on its bactericide effect (sample 31444083). The examination was carried out according to SN195924. The test-organism was lactobacillus brevis DSM 20054. As test sample a not anti-microbially equipped cotton fabric was used (Table 10). Five measurements were carried out on each sample as well as the test sample.
TABLE 10 Results of the examination of the anti-bacterial effect in a germ carrying experiment with Lactobacillus brevis as examinated germ Ig KBE after X hours of contact 0- AE-values sample 0 average 2 6 24 AE6 AE24 rating test 1 7,0 6,9 7,3 8,0 9,3 −1,1 −2,4 test 2 6,8 7,2 8,0 9,3 −1,1 −2,4 test 3 7,0 7,3 8,0 9,3 −1,1 −2,4 test 4 7,0 7,0 8,0 9,4 −1,1 −2,5 test 5 6,7 6,9 8,1 9,2 −1,2 −2,3 3144408.1 6,9 6,9 6,2 3,0 4,2 3,9 2,7 + 3144408.2 6,9 6,4 3,5 6,1 3,4 0,8 + 3144408.3 6,9 6,2 4,5 4,0 2,9 2,9 + 3144408.4 7,0 6,2 3,0 6,2 3,0 0,7 + 3144408.5 7,0 6,1 3,5 6,2 3,4 0,7 +
KBE = number of colony-building units of test-bacteria
AE = antimicrobial effect
- Evaluation-Cirteria:
- The 24-hours-value of the growth-control (control, i. e. standard-fabric) has to be larger than the initial value by at least two orders of magnitude (AE<−2).
- An antimicrobial effect is given, if a KBE-value is at most 0.5 decadic logarithms above the average value of the KBE at zero contact time, i. e. AE5.24>−0.5.
- The effect of an antimicrobial equipment is given, if for the test-bacteria 4 of 5 single KBE-values of each contact time show an antimicrobial property. These requirements are met by the results of sample number 3144408 (knitted hose).
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PCT/EP2004/003466 WO2004088009A1 (en) | 2003-04-04 | 2004-04-01 | Cellulosed molded article having a functional effect and method for producing the same |
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Also Published As
Publication number | Publication date |
---|---|
EP1611272B1 (en) | 2009-08-26 |
EP1611272A1 (en) | 2006-01-04 |
DE502004009966D1 (en) | 2009-10-08 |
JP2006522232A (en) | 2006-09-28 |
CN1816651A (en) | 2006-08-09 |
ATE440981T1 (en) | 2009-09-15 |
PL1611272T3 (en) | 2009-12-31 |
RU2005134210A (en) | 2006-05-10 |
DE10315749A1 (en) | 2004-10-14 |
RU2340710C2 (en) | 2008-12-10 |
CN100545325C (en) | 2009-09-30 |
WO2004088009A1 (en) | 2004-10-14 |
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