EP0426862A1 - Fibre et resine antibacterienne et sa production - Google Patents

Fibre et resine antibacterienne et sa production Download PDF

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Publication number
EP0426862A1
EP0426862A1 EP90904417A EP90904417A EP0426862A1 EP 0426862 A1 EP0426862 A1 EP 0426862A1 EP 90904417 A EP90904417 A EP 90904417A EP 90904417 A EP90904417 A EP 90904417A EP 0426862 A1 EP0426862 A1 EP 0426862A1
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EP
European Patent Office
Prior art keywords
silver
polyacrylonitrile
resin
polyester
water
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.)
Withdrawn
Application number
EP90904417A
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German (de)
English (en)
Other versions
EP0426862A4 (en
Inventor
Hiroyoshi 762-31 Kuraganomachi Nowatari
Yasuo 104-3 Yashiro Kuroda
Tsuyoshi Mouri
Yuji 239 Iwahanamachi Yamauchi
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2041141A external-priority patent/JP2925628B2/ja
Priority claimed from JP2044346A external-priority patent/JPH03130466A/ja
Application filed by Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Publication of EP0426862A1 publication Critical patent/EP0426862A1/fr
Publication of EP0426862A4 publication Critical patent/EP0426862A4/en
Withdrawn legal-status Critical Current

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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
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • 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
    • D06M11/83—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 metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles

Definitions

  • This invention relates to an antimicrobial polyacrylonitrile or polyester fiber or resin, and to a method in which a polyacrylonitrile or polyester fiber or resin is processed to provide antimicrobial properties.
  • antimicrobial materials have even been propagated and utilized everywhere in life. Further, they are becoming more indispensable to food industries such as meat industries, areas such as medical treatment, and manufacturing industries such as medical supplies. Furthermore, they may be considered that as society is aging, their importance will increase even more in the future.
  • PAN Polyacrylonitrile fibers or resins
  • PET polyester fibers and resins
  • the useful silver concentration range is not less than 0.1 milliequivalent (meq)/g fiber, and 0.69 meq/g fiber of silver is used in its working example. This means that a large amount of silver, i.e. 1% and 7% by weight per fiber is used, respectively. This contains a practical problem from the economic viewpoint.
  • the PET has no chemically active group in the structure thereof.
  • CDPET so-called cationic dye dyeable type polyester fibers or resins
  • CDPET so-called cationic dye dyeable type polyester fibers or resins
  • PETs having sulfonic group and/or sulfonate group in the fiber for the purpose of improving the dyeing properties have been known.
  • CDPET sulfonic group and/or sulfonate group in the fiber
  • the inventors have studied about a method for uniformly adhering or bonding to PAN or CDPET silver with avoiding the aggregation. As a result, the present invention has been accomplished.
  • This invention relates to:
  • the PANs polyacrylonitrile fibers and resins
  • the fibers or resins with the amount of sulfonic group and/or sulfonate group especially increased, but it is sufficient to use commercially available PANs having a sulfonic group and/or a sulfonate group such as Cashmilon, Toraylon, Exlan, Beslon, Vonnel, and Kanekalon.
  • resin in various forms such as sheet, powder and granule may be used as the PAN, and the PAN in any form may be treated in accordance with the method of this invention.
  • the PANs which are used in this invention usually are copolymers comprising at least 60 mol% of acrylonitrile and unsaturated compounds containing vinyl group copolymerizable with the acrylonitrile. Any PAN can be used in this invention as long as the PAN contains such an amount of sulfonic group and/or sulfonate group that 1 to 1,000 ppm or more of silver can be adhered or bonded thereto when the treatment of the above-mentioned (2), (3) or (4) is carried out.
  • CDPETs polyester fibers and resins having sulfonic group and/or sulfonate group in the structure thereof
  • the fibers or resins with the amount of sulfonic group and/or sulfonate group especially increased, and commercially available cationic dye dyeable type polyesters (CDPET) or polyester cloths or yarns mixed with raw CDPET yarns can be used.
  • CDPET cationic dye dyeable type polyesters
  • resins in various forms such as sheet, powder and granule can be used.
  • the CDPETs are polyester fibers or resins which are obtained mainly by the dehydrating polycondensation reaction of terephthalic acid and/or phthalic acid (derivatives) with polyhydric alcohols and have sulfonic group and/or sulfonate group in the structure thereof.
  • Any CDPET can be used as long as the CDPET contains such an amount of sulfonic group and/or sulfonate group that 1 to 1,000 ppm or more of silver can be adhered or bonded thereto when the treatment of the above-mentioned item (2), (3) or (4) is carried out.
  • Phthalic acid, isophthalic acid, p-hydroxybenzoic acid, 2-sulfoterephthalic acid, 5-sulfoisophthalic acid, and the like, are used as the phthalic acid (derivatives), and ethylene glycol, pentaerythritol, oligoethylene glycols and the like are used as the polyhydric alcohols.
  • the water-soluble silver compound to be used is usually silver nitrate, but other compounds such as silver fluoride, silver perchlorate, silver sulfate, silver lactate, silver tetrafluoroborate and silver acetate may also be used.
  • the glass transition temperature of the PAN depends on the kind of PAN, but generally is in the range of 60 to 90°C. Therefore, when the PAN is used, a temperature not lower than the glass transition temperature of the PAN may be obtained by setting a reaction temperature (a treating bath temperature) to not lower than 90°C in general. The reaction may also be carried out at normal pressure, while boiling the treating bath. There is also no problem in carrying out the reaction at a temperature of not lower than 100°C under pressure.
  • the reaction temperature is not specifically limited as long as it is not lower than the glass transition temperature of the PAN, but in order not to impair the characteristics of the PAN, it is preferably not higher than 130°C, especially in the range of the glass transition temperature to 100°C.
  • the glass transition temperature of the commercially available CDPET depends on the kind of CDPET, but is generally in the range of 70 to 90°C. Therefore, when the CDPET is used, a temperature not lower than the glass transition temperature of the CDPET may be obtained by setting the reaction temperature (a treating bath temperature) to not lower than 90°C in general. The reaction may be carried out at normal pressure, while boiling the treating bath. There is also no problem carrying out the reaction at a temperature of not lower than 100°C under a pressure.
  • the reaction temperature is not specifically limited as long as it is not lower than the glass transition temperature of the CDPET but in order not to impair the characteristics of the CDPET, it is preferably not higher than 200°C, especially in the range of 90 to 140°C.
  • the CDFR is added to an aqueous solution of the water-soluble silver compound, and the reaction is performed by heating it to a temperature not lower than the glass transition temperature of the CDFR added, with stirring.
  • the reaction may also be carried out by preheating an aqueous solution of the water-soluble silver compound to a temperature not lower than the glass transition temperature of the CDFR, and then adding the CDFR.
  • the bath ratio (CDFR: the aqueous solution of the water-soluble silver compound) is suitably in the range of 1 : 10 to 40 (weight ratio).
  • the heat treatment period is not specifically limited, but generally it is sufficient to carry out the heat treatment for 10 to 60 minutes.
  • the amount of the water-soluble silver compound to be added depends on the amount of silver desired to be adhered, kind of CDFR, and the reaction conditions. In the case of CDFRs which are generally commercially available, the water-soluble silver compound may be used in such an amount as 1 to 5 times the amount of silver desired to be adhered or bonded to the CDFR.
  • the PAN it is preferable in order not to impair the characteristics of the PAN, such as the feeling of the fiber, to pay attention to the control of the bath temperature after the treatment. To be specific, it is preferred to cool the bath gradually until the bath temperature becomes lower than 60°C.
  • an antimicrobial CDFR of the present invention having silver sulfonate group can be obtained.
  • the antimicrobial CDFR of the present invention having silver sulfonate group has less coloration, and has almost no tendency to color change by sunlight and reduction by detergent, thus it is very advantageous considering practical application to living hygienic fields.
  • the coloration causes a problem, such as in the case of white cloth
  • the pH adjustment can be performed by the use of a buffer, an acid or the like, but the use of a compound which reacts with silver to form a precipitate such as hydrochloric acid is not preferable.
  • the pH value is adjusted with acetic acid, lactic acid, or an acetic acid buffer.
  • the pH level preferably ranges from 1 to 5.
  • the concentration of the acid is defined by the pH.
  • the concentration of the buffer solution is not specifically limited, but generally it is sufficient to be 0.01 mol/l (acetic acid buffer) more or less.
  • the antimicrobial CDFR thus obtained, if necessary, can be further reduced to provide CDFR with fine silver particles adhered thereto.
  • a reducing agent having a relatively strong reducing power is preferably used.
  • hydroxylamine, hydrazine, glucose-caustic alkali, sodium boron hydride, or the like may be used as the reducing agent.
  • the reduction treatment can be carried out by the use of an aqueous solution of the reducing agent, preferably in a concentration in the range of 0.05 to 5% by weight preferably in an amount of 2 to 30 times the weight of the antimicrobial CDFR having silver sulfonate, and preferably heating to 95 to 100°C for five minutes or more.
  • the antimicrobial CDFR having silver sulfonate and the antimicrobial CDFR with fine silver particles adhered thereto thus obtained have a sufficient antimicrobial effect, even when silver content is a low content in the range of 1 to 1,000 ppm, preferably 10 to 1,000 ppm.
  • the resins or the fibers unexpectedly exhibit strong antimicrobial effects, and excel in wash fastness, in spite of a low content of silver in the range of 1 to 1,000 ppm. This is because, in the antimicrobial CDFR of the present invention, silver is uniformly adhered or bonded onto the fibers or resins and silver separated as metallic silver does not aggregate but exists as fine particles.
  • the antimicrobial CDFR having silver sulfonate and the pale yellow CDFR with fine silver particles adhered thereto according to the present invention can be dyed with a cationic dye in a suitable color tone by a known method. Otherwise, the CDFR may be dyed with a cationic dye by the conventional method at first, and then antimicrobial properties can be provided thereto according to the method of the present invention. Furthermore, the antimicrobial properties can be provided according to the present invention simultaneously with the dyeing using a cationic dye from which halogen ions contained have been removed carefully.
  • the antimicrobial CDFR of the present invention exhibits highly antimicrobial effects, in spite of a markedly low content of silver, it is sufficient to use a small amount of silver, and still does not adversely affect human body.
  • the antimicrobial CDFR of the present invention can be utilized as an antimicrobial material in any place which has a possibility to be contaminated with harmful microorganisms.
  • microbially clean state can be maintained by making a bath mat, a toilet mat, a toilet seat cover, a carpet, a mop, an air filter, a towel, and a dish towel.
  • the antimicrobial PAN may be used further as work gloves or work clothings in food processing or production.
  • the antimicrobial CDPET it can be used in, for example, a white overall for the operation, a curtain in hospital, a bed, a sofa, a pillow cover or a backing of a slipper equipped in hospital, or a diaper cover, a sanitary tampon and the like.
  • the antimicrobial CDFR of the present invention may be used alone or used together with other fibers as mixed or union fabric of a cloth, a knitted product, or a nonwoven material.
  • the test for antimicrobial activity was carried out by adhering bacterium, Staphylococcus aureus or Klebsiella pneumoniae , having been suspended in a standard bouillon medium, to a test strip, maintaining it at 37°C for 18 hours, and then counting the number of the living bacterium on the test strip.
  • the test for washing fastness was carried out by measuring the antimicrobial effect of a test strip which was subjected to the procedure according to JIS L 0217 103 repeatedly thirty times, and measuring the amount of remaining silver by atomic absorption spectrometry.
  • Cashmilon PAN available from Asahi Kasei Co., Ltd.
  • PAN available from Asahi Kasei Co., Ltd.
  • 3000 parts by weight of water containing 0.126 part by weight of silver nitrate 100 parts by weight of Cashmilon (PAN available from Asahi Kasei Co., Ltd.) was soaked in 3000 parts by weight of water containing 0.126 part by weight of silver nitrate. It was heated to a boil, and maintained in the boiling state for 30 minutes. Then the heating was stopped, and it was left standing until it cooled down to 50°C, after which Cashmilon was taken out. It was thoroughly washed with water and then dried, to obtain a Cashmilon having silver-sulfonate group.
  • 0.2 g of the treated cloth obtained in the above-mentioned manner was sampled, then 0.2 ml of a standard bouillon suspension of Staphylococcus aureus ATCC 6538P (the number of bacterium; 8 x 105/ml) was applied thereon. This was maintained at 37°C for 18 hours, and then it was extracted with 20 ml of physiological saline buffer containing phosphate. The extract was inoculated into a standard agar medium, and the number of bacterium was counted. As a result, the extract from the treated cloth according to the present invention was found to contain 18 bacterium/ml. In contrast, the extract from an untreated control cloth not containing silver was found to contain 9 x 103 bacterium/ml.
  • a testing cloth (a treated cloth) was obtained by following the procedure of Example A1, except that 100 parts by weight of Toraylon (PAN available from Toray Co., Ltd.) instead of Cashmilon and 0.063 part by weight of silver nitrate instead of 0.126 part by weight were used.
  • Toraylon PAN available from Toray Co., Ltd.
  • 0.063 part by weight of silver nitrate instead of 0.126 part by weight were used.
  • 35 bacterium/ml were detected from the extract and 7 x 103 bacterium/ml were detected from the extract from an untreated cloth not containing silver.
  • Testing cloths were obtained by following the procedure of Example A1, except that the amounts of silver nitrate were changed to 0.032 part by weight, and 0.008 part by weight respectively, and the test was carried out in a similar manner.
  • Example A1 to A4 are shown in Table A1.
  • Example A1 The antimicrobial activity tests were carried out in the same manner as in Example A1, except that 0.2 ml of a standard bouillon suspension of Klebsiella pneumoniae ATCC 4352 (number of bacterium: 9 x 105/ml) in place of Staphylococcus aureus was applied on each of the cloths to which silver was adhered or bonded and which were obtained in Examples A1, A3, A5 and A7. The results are shown in Table A4. The extract from the untreated control cloth not containing silver contained 1 X 104 bacterium/ml.
  • Example A1 The antimicrobial activity test was examined for the testing strip obtained in the same manner as in Example A1 except that 0.124 part by weight of silver lactate was used in place of silver nitrate. The results obtained were substantially the same as those of Example A1.
  • a testing cloth was obtained in the same manner as in Example A5, except that 2.5 parts by weight of hydroxyl amine or 2.5 parts by weight of hydrazine was used in place of sodium boron hydride, and the antimicrobial activity test was examined. In each case, the results obtained were substantially the same as those of Example A5.
  • Exlan PAN available from Nihon Exlan Co., Ltd.
  • Exlan PAN available from Nihon Exlan Co., Ltd.
  • the content of silver in this polyacrylonitrile cloth was 374 ppm.
  • ⁇ L, ⁇ a, and ⁇ b represent lightness difference, hue difference, and saturation difference between the treated cloth and the untreated cloth, respectively.
  • an antimicrobial polyacrylonitrile cloth without any color tone variation can be obtained by conducting the reaction in an acidic aqueous solution by adjusting the pH value.
  • Toraylon PAN available from Toray Co., Ltd.
  • Toraylon PAN available from Toray Co., Ltd.
  • sulfonate group 120 parts by weight of Toraylon (PAN available from Toray Co., Ltd.) having sulfonate group was soaked in 3,600 parts by weight of water in which 0.24 part by weight of silver nitrate was dissolved. It was then gradually heated to a boil, maintained for 30 minutes, and then the Toraylon was taken out and washed with water.
  • 0.2 g of a test strip was sampled from the cloth obtained in the above-mentioned manner, and 0.2 ml of a standard bouillon suspension of Klebsiella pneumoniae ATCC4352 (the number of bacterium; 9 x 105/ml) was applied thereon. This was maintained at 37°C for 18 hours, and then it was extracted with 20 ml of physiological saline buffer containing phosphate. As a result, the extract from the treated cloth according to the present invention was found to contain 43 bacterium/ml. In contrast, the extract from an untreated control cloth not containing silver was found to contain 1 x 104 bacterium/ml.
  • Toraylon PAN available from Toray Co., Ltd.
  • the bath ratio was 1 : 30.
  • the red dyed cloth was soaked in 1200 parts by weight of water-containing 0.2 part by weight of silver nitrate. It was then gradually heated, and boiled for 30 minutes. Thereafter, it was thoroughly washed with boiling water.
  • Example A1 The treatment of Example A1 was repeated except that particles of polyacrylonitrile having sulfonate group were treated instead of Cashmilon in Example A1.
  • the treated polyacrylonitrile particle exhibited antimicrobial effect similar to those of Example A1.
  • 0.2 g of the cloth obtained in the above-mentioned manner was sampled and 0.2 ml of a standard bouillon suspension of Staphylococcus aureus ATCC 6583P (the number of bacterium; 8 x 105/ml) was applied thereto. This was maintained at 37°C for 18 hours, and then it was extracted with 20 ml of physiological saline buffer containing phosphate. The extract was inoculated into a standard agar medium, and the number of bacterium was counted. As a result, the extract from the treated cloth according to the present invention was found to contain 120 bacterium/ml. In contrast, the extract from an untreated control cloth not containing silver was found to contain 6 x 108 bacterium/ml.
  • Treated cloths respectively containing specific amount of silver were obtained by following the procedure of Example B1, except that 0.09 part by weight, 0.045 part by weight, and 0.01 part by weight of silver nitrate were respectively used instead of 0.18 part by weight of silver nitrate. They were evaluated in a similar manner as in Example B1. The results are shown in Table B1.
  • Example B4 The antimicrobial activity tests were carried out in the same manner as in Example B1, except that 0.2 ml of a standard bouillon suspension of Klebsiella pneumoniae ATCC 4352 (number of bacterium: 9 X 105/ml) in place of Staphylococcus aureus was applied on each of the treated cloths obtained in Examples B1, B3, B5 and B7.
  • the extract from the untreated control cloth not containing silver contained 8 x 108 bacterium/ml. The results are shown in Table B4.
  • Example B1 The antimicrobial activity test was carried out on the strip obtained in the same manner as in Example B1 except that 0.17 part by weight of silver lactate was used in place of silver nitrate in Example B1. The results obtained were substantially the same as those of Example B1.
  • Example B5 A test cloth was obtained in the same manner as in Example B5, except that 500 parts by weight of an aqueous 0.5% hydrazine solution or 500 parts by weight of 0.5% sodium boron hydride suspension was used in place of hydroxylamine in Example B5, and the antimicrobial activity test was carried out. In each case, the results obtained were substantially the same as those of Example B5.
  • a cationic dye dyeable type polyester having sulfonate group (a standard dyeing temperature: 105°C) was soaked in 2,500 parts by weight of water containing 0.05 part of silver nitrate, and heated to boil with stirring. After stirring for another 20 minutes, it was allowed to cool, thoroughly washed with water, and dried to obtain a polyester cloth having silver sulfonate group.
  • the content of silver in this polyester cloth was measured by atomic absorption spectrometry, it was found to contain 301 ppm of silver.
  • the silver content in the polyester cloth after washing 30 times as in Example B9 was 290 ppm.
  • the extract from the unwashed cloth was found to contain 135 bacterium/ml and the extract from the polyester cloth after washing 30 times was found to contain 118 bacterium/ml, while the untreated polyester cloth for control which did not contain silver was found to contain 7 x 108 bacterium/ml.
  • the content of silver in this polyester cloth was 354 ppm.
  • ⁇ L, ⁇ a, and ⁇ b represent lightness difference, hue difference, and saturation difference between the treated cloth and the untreated cloth, respectively.
  • the red dyed cloth was soaked in 1,200 parts by weight of water containing 0.2 part by weight of silver nitrate, and gradually heated to a boil, and maintained for 30 minutes. Thereafter, it was thoroughly washed with boiling water and then dried to obtain a polyester having silver-sulfonate group.
  • the polyester thus treated also had a high antimicrobial activity against Staphylococcus aureus and Klebsiella pneumoniae .
  • Example B5 35 parts by weight of the cationic dye dyeable polyester with fine particles of silver adhered thereon obtained in Example B5 was soaked in 400 parts by weight of water in which 0.07 part by weight of a cationic dye, Kayacryl blue 4GSL, had been dissolved. It was heated to 120°C in an autoclave, and maintained for 40 minutes to carry out dyeing. After cooling, the dyed cloth was taken out, and thoroughly washed with water to obtain a blue dyed polyester cloth. The antimicrobial activity was retained.
  • a cationic dye Kayacryl blue 4GSL
  • Example B1 The treatment of Example B1 was carried out except that a polyester resin particle having sulfonate group was used instead of the cationic dye dyeable polyester cloth in Example B1.
  • the resultant polyester resin particle exhibited antimicrobial effects similar to those of Example B1.
  • the antimicrobial CDFR of the present invention in spite of a smaller amount of silver to be adhered or bonded than that of the conventional one, exhibits strong antimicrobial effects, and excels in wash fastness.
  • the antimicrobial CDFR of the present invention also is very safe, and when incinerating it, it is free from generating any toxic substance derived from the substance used for providing antimicrobial activity.
  • the antimicrobial CDFR of the present invention has a markedly low stimulation on skin, thus it can also suitably be used in such an application as bringing it into contact with skin such as clothes.
  • antimicrobial properties can be easily and economically provided to PAN and CDPET having sulfonic group and/or sulfonate group or fibers mixed or combined with, PAN or CDPET.
  • PAN and CDPET having sulfonic group and/or sulfonate group or fibers mixed or combined with, PAN or CDPET.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

La présente invention se rapporte (1) à une fibre et une résine antibactériennes en polyacrylonitrile ou polyester contenant de 1 à 1000 ppm, de préférence de 10 à 1000 ppm, d'argent sous forme de sulfonate d'argent, (2) à un procédé de production de la fibre ou de la résine antibactériennes en polyacrylonitrile ou polyester consistant à faire réagir dans l'eau ladite fibre ou résine présentant des groupes sulfo et/ou sulfonate dans sa structure avec un composé d'argent soluble dans l'eau, ce procédé se caractérisant par le fait que ladite réaction a lieu à une température supérieure au point de transition vitreuse du polyacrylonitrile ou du polyester, (3) à un procédé de production de la fibre ou de la résine antibactériennes en polyacrylonitrile ou polyester consistant à faire réagir dans l'eau ladite fibre ou résine présentant des groupes sulfo et/ou sulfonate dans sa structure avec un composé d'argent soluble dans l'eau, ce procédé se caractérisant par le fait que ladite réaction a lieu à une température supérieure au point de transition vitreuse du polyacrylonitrile ou du polyester, et à traiter le produit de réaction avec un agent réducteur, et (4) à une fibre et une résine antibactériennes en polyacrylonitrile ou polyester produites grâce au procédé (2) ou (3) susmentionné.
EP19900904417 1989-03-08 1990-03-07 Antibacterial fiber and resin and production thereof Withdrawn EP0426862A4 (en)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
JP5390389 1989-03-08
JP53904/89 1989-03-08
JP5390489 1989-03-08
JP53903/89 1989-03-08
JP184441/89 1989-07-19
JP18444189 1989-07-19
JP184442/89 1989-07-19
JP18444289 1989-07-19
JP41141/90 1990-02-23
JP2041141A JP2925628B2 (ja) 1989-03-08 1990-02-23 抗菌性繊維の製造方法
JP44346/90 1990-02-27
JP2044346A JPH03130466A (ja) 1989-03-08 1990-02-27 抗菌性繊維、樹脂及びその製造方法

Publications (2)

Publication Number Publication Date
EP0426862A1 true EP0426862A1 (fr) 1991-05-15
EP0426862A4 EP0426862A4 (en) 1992-01-02

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EP19900904417 Withdrawn EP0426862A4 (en) 1989-03-08 1990-03-07 Antibacterial fiber and resin and production thereof

Country Status (3)

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EP (1) EP0426862A4 (fr)
CA (1) CA2028131A1 (fr)
WO (1) WO1990010746A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996000321A1 (fr) * 1994-06-24 1996-01-04 Suntory Limited Fibre antibacterienne, textile et element de traitement des eaux a base de cette fibre et procede de production
EP0783048A3 (fr) * 1995-12-29 1998-01-14 Japan Exlan Company, Ltd. Fibres contenant des particules métalliques fines et procédé pour leur fabrication
EP1380673A1 (fr) * 2002-07-12 2004-01-14 Japan Exlan Co., Ltd. Inhibiteur de décoloration pour métaux
EP1830000A1 (fr) * 2006-03-01 2007-09-05 Rebac Gmbh Matériel antimicrobien contenant du polyacrylonitrile et des cations metalliques et non-metalliques liés au mème
US20210145097A1 (en) * 2018-04-20 2021-05-20 Accel Lifestyle, Llc Antimicrobial silver fiber products and methods of manufacturing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6849462B1 (en) 1991-11-22 2005-02-01 Affymetrix, Inc. Combinatorial strategies for polymer synthesis
US6943034B1 (en) 1991-11-22 2005-09-13 Affymetrix, Inc. Combinatorial strategies for polymer synthesis
CN112680844A (zh) * 2020-11-30 2021-04-20 上海亮丰新材料科技有限公司 一种草珊瑚植物抗菌调温纱线、面料及制备方法

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Publication number Priority date Publication date Assignee Title
JPS55137210A (en) * 1979-04-05 1980-10-25 Mitsubishi Rayon Co Ltd Antimicrobial fiber
JPS56148965A (en) * 1980-04-17 1981-11-18 Mitsubishi Rayon Co Durable sterilizable fiber
DE3209796A1 (de) * 1982-03-18 1983-10-13 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von faeden und fasern aus acrylnitrilpolymerisaten
JPH05292000A (ja) * 1992-04-10 1993-11-05 Japan Radio Co Ltd スペクトラム拡散衛星信号受信装置の異常検出方法及びスペクトラム拡散衛星信号受信装置

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996000321A1 (fr) * 1994-06-24 1996-01-04 Suntory Limited Fibre antibacterienne, textile et element de traitement des eaux a base de cette fibre et procede de production
EP0783048A3 (fr) * 1995-12-29 1998-01-14 Japan Exlan Company, Ltd. Fibres contenant des particules métalliques fines et procédé pour leur fabrication
US5897673A (en) * 1995-12-29 1999-04-27 Japan Exlan Company Limited Fine metallic particles-containing fibers and method for producing the same
EP1380673A1 (fr) * 2002-07-12 2004-01-14 Japan Exlan Co., Ltd. Inhibiteur de décoloration pour métaux
EP1830000A1 (fr) * 2006-03-01 2007-09-05 Rebac Gmbh Matériel antimicrobien contenant du polyacrylonitrile et des cations metalliques et non-metalliques liés au mème
US20210145097A1 (en) * 2018-04-20 2021-05-20 Accel Lifestyle, Llc Antimicrobial silver fiber products and methods of manufacturing the same

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Publication number Publication date
EP0426862A4 (en) 1992-01-02
WO1990010746A1 (fr) 1990-09-20
CA2028131A1 (fr) 1990-09-09

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