CN1831232A - Method with antibiotic and antifungal property for fabric construction - Google Patents

Method with antibiotic and antifungal property for fabric construction Download PDF

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Publication number
CN1831232A
CN1831232A CNA2005100924640A CN200510092464A CN1831232A CN 1831232 A CN1831232 A CN 1831232A CN A2005100924640 A CNA2005100924640 A CN A2005100924640A CN 200510092464 A CN200510092464 A CN 200510092464A CN 1831232 A CN1831232 A CN 1831232A
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CN
China
Prior art keywords
fiber
silver
fibrous structure
structure thing
antibiotic
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Chinese (zh)
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中川哲男
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Japan Exlan Co Ltd
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Japan Exlan Co Ltd
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    • 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
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D1/00—Woven fabrics designed to make specified articles
    • D03D1/0017—Woven household fabrics
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D1/00—Woven fabrics designed to make specified articles
    • D03D1/06—Curtain heading tapes
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/208—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based
    • D03D15/217—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based natural from plants, e.g. cotton
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • 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
    • D06M11/58—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 nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64—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 nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
    • D06M11/65—Salts of oxyacids of nitrogen
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/13—Physical properties anti-allergenic or anti-bacterial
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/02—Underwear
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/02—Underwear
    • D10B2501/021—Hosiery; Panti-hose
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/04—Outerwear; Protective garments
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/04—Outerwear; Protective garments
    • D10B2501/041—Gloves
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/04—Outerwear; Protective garments
    • D10B2501/043—Footwear
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2503/00—Domestic or personal
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2509/00—Medical; Hygiene
    • D10B2509/02—Bandages, dressings or absorbent pads
    • D10B2509/026—Absorbent pads; Tampons; Laundry; Towels

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Botany (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Artificial Filaments (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Gloves (AREA)
  • Undergarments, Swaddling Clothes, Handkerchiefs Or Underwear Materials (AREA)

Abstract

The present invention relates to method for fiber structure to possess antibiotic and mold-proof performance and thus obtained fiber product. Great efforts have been made for giving fiber structure with antibiotic and mold-proof performance, and up to now, satisfactory antibiotic and mold-proof performance has not been obtained. The present invention aims at providing method for fiber structure to possess antibiotic and mold-proof performance while maintaining the texture, hygroscopicity, water absorption and other performance of the fiber structure without degradation. The method includes heat treatment of acrylonitrile fiber containing silver compound at pH 1-6 to form silver supporting acrylonitrile fiber and constituting fiber structure with the silver supporting acrylonitrile fiber in the content of 5-15 wt%.

Description

Give the method for the antibiotic anti-fungi performance of fibrous structure thing
Technical field
The method and containing that the present invention relates to give the antibiotic anti-fungi performance of fibrous structure thing adopts the fibre of the fibrous structure thing that this method obtains.
Background technology
In recent years,, the expectation of keeping, strengthening of health is improved, wish to occur cleaning more, comfortable dress material, nightwear, underwear product or the means of livelihood etc. along with the tendency of the abundant and comfortable living environment of progress, the demand of the maturing of society and aging.Actively carry out as realizing such cleaning, the behavior that comfortable means are given antibiotic anti-fungi performance.
For example in patent documentation 1, the solution that discloses the multifunctional acylate that makes the didecyl dimethylamino contains the manufacture method of the anti-microbial property fiber that is immersed in the fiber.The such quaternary ammonium salt of multifunctional acylate of didecyl dimethylamino is organic class antiseptic, and processability well just is used more all the time, exists in the occasion of cyclic washing to come off the problem that antibiotic anti-fungi performance fades away.
In addition, following antibiotic processing method is disclosed in patent documentation 2: antibiotic property metals such as silver are supported on inorganic supporting such as zeolite or apatite form inorganic antiseptic on the body, with inorganic dispersant this inorganic antiseptic is dispersed in the antibiotic processing agent of formation in the water, in the presence of cationic surfactant, fabric is contained and be immersed in this antibiotic processing agent.Fibre ratio by this processing method processing uses the occasion of adhesive to improve the quality sense, but does not but avoid the situation than the quality reduction of the fabric before the processing.In addition, also there is by inorganic antiseptics such as frictions to come off the problem that effect reduces easily.
Further, following method is disclosed in patent documentation 3: with the inorganic antiseptic that supports silver ion in activated carbon or the zeolite mixing in synthetic fiber such as polyester antibiotic fiber and cotton fiber blending or the manufacture method of mixing the antibiotic fiber goods knit.But,, have to mix the antibiotic fiber of a great deal of in order to obtain composite rate that enough antibacterial effects need antibiotic fiber at least more than 2 one-tenth.Therefore, a lot of problem of characteristic infringement that has quality, dyeability and the hygroscopicity etc. that derive from cotton fiber.
[patent documentation 1] spy opens flat 10-331069 communique
[patent documentation 2] spy opens the 2002-370911 communique
[patent documentation 3] spy opens flat 7-109672 communique
Summary of the invention
As above-mentioned, up to now giving antibiotic anti-fungi performance to the fibrous structure thing also carries out actively making great efforts, also considering can not provide very satisfied performance because problems such as antibiotic anti-fungi performance reduction that washing etc. bring and quality reduction are added desired performance High Level.The invention that the present invention carries out in view of this present situation, purpose provide each performance such as the quality that do not make the fibrous structure thing, hygroscopicity, water imbibition and reduce, the method for giving antibiotic anti-fungi performance to this fibrous structure thing.
The result that the inventor furthers investigate has in order to achieve the above object reached the present invention shown below.
That is, the present invention is made of following means.
(1) gives the method for the antibiotic anti-fungi performance of fibrous structure thing, it is characterized in that, the acrylic fiber that contains silver-colored compounds is implemented heat treatment formation support silver-colored acrylic fiber in the scope of pH1-6, with its formation fiber as the fibrous structure thing, making its content is 5-15 weight %.
(2) (1) described methods of giving the antibiotic anti-fungi performance of fibrous structure thing is characterized in that the acrylic fiber with silver-colored compounds has anionic property functional group.
(3) (1) or (2) described method of giving the antibiotic anti-fungi performance of fibrous structure thing, it is characterized in that heat treatment is 100-160 ℃ damp and hot or dry heat treatment.
The described method of giving the antibiotic anti-fungi performance of fibrous structure thing of each of (4) (1)-(3) is characterized in that, the silver content that supports the acrylic fiber of silver is 1-100mmol/kg.
The described method of giving the antibiotic anti-fungi performance of fibrous structure thing of each of (5) (1)-(4) is characterized in that the fibrous structure thing contains cotton fiber.
(6) fibre, at least a portion have the fibrous structure thing of giving antibiotic anti-fungi performance with each described adding method of above-mentioned (1)-(5).
(7) (6) described fibres, it is characterized in that fibre is selected from inner lining material, pyjamas, bathing gown, towel, bath mat, carpet, felt, bedding, curtain, the chair lining cloth (Zhang り ground) of undershirt, loincloth, motion body harness, mouth mask, handbag, socks, stocking, the stocking sole, footwear.
According to the present invention, to various fibrous structure things such as undershirt, loincloth, motion body harness, mouth mask, handbag, socks, stocking, pyjamas, bathing gown, towel, bath mat, carpet, felt, bedding, curtain, chair lining cloth, do not damage the feature that the fibrous structure thing just had originally, give the antibiotic anti-fungi performance of good endurance.That is, the antibiotic anti-fungi performance excellence of acrylic fiber that supports silver that the present invention adopts is penetrated by illumination in addition and can also be improved antibiotic anti-fungi performance,, also has so-called photocatalytic activity, so just can obtain effect of sufficient with a small amount of use that is.In addition, because the silver content that supports in the silver-colored acrylic fiber is few, so almost also do not cause painted.Further, this fiber is than organic class antiseptic durability height such as quaternary ammoniums, so even the antibiotic anti-fungi performance of fibrous structure thing cyclic washing that obtains according to the present invention does not reduce yet.
The specific embodiment
Below describe the present invention in detail.Among the present invention,, adopt the silver-colored acrylic fiber that supports of the acrylic fiber that contains silver-colored compounds being implemented heat treatment formation in the scope of pH1-6 as the active ingredient of the antibiotic anti-fungi performance of performance.This fiber is given photocatalytic activity by heat treatment, with the acrylic fiber comparison that contains silver-colored compounds before the heat treatment, is the fiber that shows higher antibiotic anti-fungi performance.Therefore, in the fibrous structure thing, can obtain effect of sufficient even without containing in a large number also, can show effect of sufficient that existing antibiotic fiber is difficult to obtain, with the antibiotic anti-fungi performance of a small amount of interpolation.So long as common occasion, the formation proportion of fibers of fibrous structure thing contains 5-15 weight %, and preferred 7-10 weight % gets final product, even the content of less than 10 weight % also can obtain effect.Like this, because it is also passable on a small quantity to support the content of silver-colored acrylic fiber, so the characteristic of the quality of the fibrous structure thing contain this fiber and dyeability etc. is adopted in influence hardly, former state is kept the characteristic that the fibrous structure thing itself has, and gives antibiotic anti-fungi performance.
So-called fibrous structure thing of the present invention is meant the general name of the complex that the yarn, sand line, filament, volume thing, fabric, nonwoven fabric, paper shape thing, tablet, sandwich, cotton shape body and their composition that adopt usual method to make constitutes.
The acrylic fiber that contains as the above-mentioned silver-colored compounds that supports silver-colored acrylic fiber raw material is the fiber that is formed by the propenyl base polymer, just have no particular limits so long as contain the fiber of silver-colored compounds, this vinyl cyanide condensate can use preferably more than 60 weight %, more preferably the acrylonitrile more than 80 weight % and the copolymer of known monomer.
The monomer of using as copolymerization so long as just there is no particular limitation with the monomer of the copolymerization of acrylonitrile of polymerism unsaturated ethylene ene compound etc., can use the vinyl esters of vinyl acetate for example etc.; Ethylene halide or ethenylidene classes such as ethlyene dichloride, ethylene bromide, vinylidene chloride; (methyl) alkyl acrylate of methyl acrylate, methyl methacrylate etc. (below, (methyl) acrylic acid record is as these two material of performance acrylic acid and methacrylic acid); The acrylic amide of (methyl) acrylamide etc.; The monomer that contains the benzene sulfonic acid base of styrene, sodium methallyl sulfonate, 2-acrylamide-2-methyl propane sulfonic acid, sodium p styrene sulfonate, sodium vinyl sulfonate etc.; (methyl) acrylic acid, maleic acid etc. contain carboxylic acid group's monomer etc., in order to contain silver-colored compounds effectively, wish to contain the monomer that contains anionic property functional group of the monomer that contains sulfonic group or carboxyl etc. of 0.1-20 weight %.
As the amount that should be contained in the silver-colored compounds in the fiber, there is no particular limitation, the preferred 1-100mmol/kg of silver content, more preferably 1-50mmol/kg in the acrylic fiber that supports silver that finally obtains.Like this, can obtain sufficient antibiotic anti-fungi performance with a spot of silver content, thus cause hardly since fiber heating or through the time change the coloring problem that produces, cost control also low, industrial also favourable.
As the method that should the silver compounds be contained in the acrylic fiber, have no particular limits, for example can enumerate the spy and open disclosed method in the flat 3-199418 communique, promptly when making acrylic fiber, processing drying continuously, heat relax the gelatine structure fiber before the operation in the silver-colored class aqueous solution, make silver-colored compounds be contained in method in the fiber, the spy opens disclosed method in clear 52-92000 communique and the flat 7-243169 communique of Te Kai, promptly, after usual way manufacturing acrylic fiber, contain the method for silver-colored compounds by back processing.
The acrylic fiber that supports silver that the present invention adopts can obtain by the above-mentioned acrylic fiber that contains silver-colored compounds that obtains is like that implemented heat treatment in the scope of pH1-6, preferred pH2-4.There is no particular limitation as this heat-treating methods, preferably 100-160 ℃ the damp and hot or xeothermic method of handling down, the acrylic fiber that for example will contain silver-colored compounds is immersed in the acidic aqueous solution of pH1-6, the fiber of removing behind the moisture is carried out the method for humid heat treatment by steam in autoclave, or will remove fiber former state behind the moisture with the withering method of dry-air blast drying machine etc.Processing time is set by investigating treatment temperature in addition.
Here, the occasion of pH less than 1 during heat treatment significantly hinders fibrous physical property, and pH surpasses 6 occasion, can not give photocatalytic activity.So in addition, heat treatment temperature is in the occasion of 100 ℃ of less thaies, and the processing time is elongated, is not industrial advantageous method, surpasses 160 ℃ occasion, hinders rerum naturas such as the form and aspect of the acrylic fiber that supports silver and the strong degree of depth not preferred.
The acrylic fiber that supports silver that as above obtains is contained fibrous structure object space method, and there is no particular limitation, carries out with the mixed cotton of other fibers, blending, mixes to knit etc. it is contained in the fibrous structure thing.In addition, there is no particular limitation as other fiber, so long as natural fabrics such as normally used cotton, fiber crops, thin,tough silk, wool, artificial silk, the regenerated fiber of cuprammonium rayon etc., the normally used fibers such as synthetic fiber of acrylic acid, nylon, polyester, vinylon etc. are just passable.
Especially, other fibers are cotton occasions, that is, to the occasion of giving antibiotic anti-fungi performance based on the fibrous structure thing of cotton fiber, method of giving antibiotic anti-fungi performance of the present invention is suitable.Cotton fiber has for the skin softness and is rich in absorbefacient character, thus in various fibrous structure things processing and utilization, have easily subsidiary mould shortcoming on the other hand.The method according to this invention because it is few to support the content of acrylic fiber of silver, so can produce cotton fiber to the skin softness be rich in absorptive character such give antibiotic anti-fungi performance.Think to utilize in this wise the occasion of the feature of cotton fiber, the content of the cotton fiber in the fibrous structure thing is desirably in 50-95 weight %, preferred 85-95 weight %.
As the fibrous structure thing that obtains by above-described method of the present invention, can enumerate the complex of yarn, sand line, filament, fabric, volume thing, nonwoven fabric, paper shape thing, tablet, sandwich, cotton shape body and their composition etc.Such fibrous structure thing directly or by further processing can be fit to use towel, clothing class, application class, footwear etc. directly contact with skin or particle-bound bacteria or mould goods in.As concrete goods, can enumerate inner lining material, pyjamas, bathing gown, towel, bath mat, carpet, felt, bedding, curtain, chair lining cloth of undershirt, loincloth, motion body harness, mouth mask, handbag, socks, stocking, the stocking sole, footwear etc.
[embodiment]
Below in order easily to understand the present invention, embodiment is shown, but these examples just at most, purport of the present invention is not subjected to these qualifications.In addition, " part " and " percentage " is represented with weight basis when being not particularly limited among the embodiment.In addition, silver content described in the following manufacture method and antibiotic anti-fungi performance are measured with following method.
(1) silver content
To use Japanese ジ ヤ-レ Le ア Star シ ユ (strain) system atomic absorption spectrum analysing arrangement AA855 type to measure the atom absorbance and try to achieve with the solution that the concentrated nitric acid solution wet type of 95% the concentrated sulfuric acid and 62% is decomposed sample fiber 0.1g.
(2) anti-microbial property
Based on the quantitative test (bacterium liquid absorption process) of JIS L1902, try to achieve bactericidal activity value and bacteriostatic activity value by following numerical expression.In addition, the mensuration of viable count is released plating method enforcement with mixing, and does not use standard cotton cloth as there being processing cloth.
Bactericidal activity value=logA-logC
Different bacterium activity value=logB-logC
Here, A=reclaims does not have processing cloth postvaccinal bacterium number at once, and B=reclaims the bacterium number that does not have after processing cloth was cultivated in 18 hours, and C=reclaims the bacterium number after processing cloth was cultivated in 18 hours.The fibre Valuation Standard of estimation of fibres technological associations of civic organization is set the different bacterium activity value of antibacterial deodourizing processing greater than 2.2, and the bactericidal activity value of system bacterium processing (general service) is more than or equal to 0.
(3) fungus resistance
Bacterium liquid with the modulation of 1/20 Sa Shi fluid nutrient medium is inoculated in the sample, measures 18 hours viable counts on the sample after the cultivation in 27 ± 1 ℃ incubator.
(4) washing methods
The test method that No. 103, employing JIS L0217 is implemented.JAFET standard lotion is used in washing.
[Production Example 1 that contains the acrylic fiber of silver-colored compounds]
Will according to the well-established law polymerization obtain by acrylonitrile 91.1%, methyl acrylate 8.6%, the vinyl cyanide condensate that sodium methallyl sulfonate 0.3% constitutes is dissolved in the sodium thiocyanate water solution of concentration 45%, makes polymer concentration at 12% spinning solution.10%, use known nozzle to extrude in-3 ℃ the sodium thiocyanate water solution this stoste, wash, extend, acrylic fiber (fiber A) is made in heat treatment.Then, for silver being imported in this fiber, 100g fiber A is put into the silver nitrate aqueous solution 1000ml that will be modulated to 20mmol/L with 1% aqueous solution of nitric acid adjust in the solution of pH3, carry out handling washing in 10 minutes at 98 ℃, after the drying, put among the sodium oxalate aqueous solution 1000ml that is adjusted into 10mmol/L, carry out handling washing in 10 minutes at 98 ℃, drying is made the acrylic fiber (fiber B) that contains silver-colored compounds.
[Production Example 2 that contains the acrylic fiber of silver-colored compounds]
Except using the vinyl cyanide polymer that constitutes by AN95%, vinyl acetate 5%, beyond will being set at 30 minutes the processing time in silver nitrate aqueous solution, same with the Production Example 1 of the acrylic fiber that contains silver-colored compounds, make the acrylic fiber (fiber C) that contains silver-colored compounds.
Will be as the acrylic fiber that contains silver-colored compounds (the fiber B of above-mentioned acquisition, C) after being immersed in the aqueous solution of adjusting pH, remove moisture, put into autoclave (heat treatment temperature surpasses 100 ℃ occasion) or air drier (occasion of heat treatment temperature below 100 ℃), 6 kinds of fibers of fiber No.1-6 are made in heat treatment under pH as shown in table 1, temperature.Fiber No.7 be contain silver-colored compounds acrylic fiber Production Example 1 the acrylic fiber that contains silver-colored compounds (fiber B) itself.
Table 1
Fiber No. Kinds of fibers Heat treatment pH Heat treatment temperature (℃) Anionic property functional group Silver content (mmol/kg)
1 Fiber B 1 120 Have 42
2 Fiber B 3 120 Have 43
3 Fiber B 3 95 Have 43
4 Fiber C 3 150 Do not have 39
5 Fiber C 3 170 Do not have 40
6 Fiber B 7 105 Have 43
7 Fiber B Do not have Do not have Have 44
[embodiment 1-5, comparative example 1-2]
For fiber No.1-7, mixed cotton during with separately fiber 10% and cotton 90% weaving obtains the braided wire of yarn count 20/1 with the cotton spinning method according to well-established law.After this braided wire carried out airing and handle with the doff shape, use terry cloth loom to make towel.For the towel that makes, adopt staphylococcus aureus (Staphylococcus aureus ATCC6538P, logA=4.3, logB=7.0) and Escherichia coli (Escherichia coli NBRC 3301, logA=4.4 logB=7.5) estimates anti-microbial property, and the result is as shown in table 2.
[table 2]
Fiber No. Staphylococcus aureus Escherichia coli
logC The bactericidal activity value The bacteriostatic activity value logC The bactericidal activity value The bacteriostatic activity value
Embodiment 1 1 1.6 2.7 5.4 1.6 2.8 5.9
Embodiment 2 2 1.3 3.0 5.7 1.3 3.1 6.2
Embodiment 3 3 2.4 1.9 4.6 2.5 1.9 5.0
Embodiment 4 4 2.7 1.6 4.3 2.6 1.8 4.9
Embodiment 5 5 2.7 1.6 4.3 2.6 1.8 4.9
Comparative example 1 6 3.8 0.5 3.2 3.8 0.6 3.7
Comparative example 2 7 4.6 -0.3 2.4 4.7 -0.3 2.8
Each bactericidal activity value surpasses the proliferation inhibiting effect of bacterium all widely more than 0 among the embodiment 1-5, has obtained to make the effect of bacterial population minimizing,, has obtained system bacterium effect that is.On the other hand, though the fiber No.6 that uses in the comparative example 1 has implemented heat treatment, treatment temperature is low, and pH is set at 7, and the result thinks can not give sufficient photocatalytic activity, is the low fiber of anti-microbial property.In addition, the fiber No.7 that uses in the comparative example 2 so can not give photocatalytic activity, can not reach the level of system bacterium processing owing to do not implement heat treatment.
[embodiment 6-7, comparative example 3-4]
Mixed cotton fiber No.2 and the cotton, similarly to Example 1, make towel when weaving with the ratio shown in the table 3.For the towel that obtains, (Staphylococcus aureus ATCC 6538P, logA=4.3 logB=7.0) estimate anti-microbial property, and the result is as shown in table 3 to adopt staphylococcus aureus.
Table 3
Fiber No.2 (weight %) Cotton (weight %) logC The bactericidal activity value The bacteriostatic activity value
Comparative example 3 2 98 4.4 -0.1 3.6
Embodiment 6 5 95 2.0 2.3 5.0
Embodiment 7 15 85 1.0 3.3 6.0
Comparative example 4 20 80 0.9 3.4 6.1
In the comparative example 3, because it is few to support the content of silver-colored acrylic fiber, so think that anti-microbial property reduces.On the other hand, content owing to the acrylic fiber that supports silver in the comparative example 4 is many, so anti-microbial property uprises, but compare with embodiment 7, content poor for the acrylic fiber that supports silver, the difference of anti-microbial property is very little, and containing the acrylic fiber that supports silver does not have effect above 15 weight %.
[embodiment 8-10]
As the Production Example 1 of the acrylic fiber that contains silver-colored compounds of above-mentioned acquisition in, as table 4, change the concentration of silver nitrate aqueous solution, in addition, obtain to contain the acrylic fiber of silver-colored compounds with method, after this fiber impregnation is in the aqueous solution of adjusting pH with nitric acid, remove moisture, put into autoclave in pH3,120 ℃ of following heat treatments of temperature, make 3 kinds of fibers of fiber No.8-10, measure the content of silver.For these fibers, similarly to Example 1, make towel in addition, (Staphylococcus aureus ATCC6538P, logA=4.3 logB=7.0) estimate anti-microbial property to adopt staphylococcus aureus.The result is as shown in table 4.
Table 4
Fiber No. Silver nitrate aqueous solution concentration (mmol/l) Silver content (mmol/kg) logC The bactericidal activity value The bacteriostatic activity value
Embodiment 8 8 5 11 2.8 1.5 4.2
Embodiment 9 9 10 21 2.0 2.3 5.0
Embodiment 10 10 50 112 0.8 3.5 6.2
As table 4 as can be known, the increase anti-microbial property that is accompanied by silver content improves, and has obtained practical anti-microbial property in the few embodiment 8 of silver content.Obtained high anti-microbial property among the embodiment 10 in addition, the fiber No.10 of use finds more only painted.These think it may is because the result of painted obviousization during the high heat treated of silver content.
[embodiment 10]
The acrylic fiber K8G0-1.7T38 mixed cotton that fiber No.2 with 12%, 88% Japanese エ Network ス ラ Application Industrial Co., Ltd make according to the well-established law weaving, is made the braided wire of cotton number 30/1.With well-established law kapok blending product colouring method (acrylic fiber: cation dyes, cotton: reactive dye) dye black.The line that braiding obtains according to well-established law is made socks.Adopt staphylococcus aureus (Staphylococcus aureus ATCC6538P for the socks that obtain, logA=4.2, logB=7.0) and pneumobacillus (Klebsiella pneumoniaeATCC 4352, logA=4.4, logB=7.4) estimate before the washing and washing 10 times after anti-microbial property.As shown in table 5, the socks that make have excellent antibiotic property.
Table 5
Washing times (inferior) logC The bactericidal activity value The bacteriostatic activity value
Staphylococcus aureus 0 1.3 2.9 5.7
10 1.3 2.9 5.7
Pneumobacillus 0 1.3 3.1 6.1
10 1.9 2.5 5.5
[embodiment 11]
The suction acrylic fiber K626-1.7T51 mixed cotton that the acrylic fiber K85-1.3T51 that fiber No.2 with 10%, 40% Japanese エ Network ス ラ Application Industrial Co., Ltd make and this Co., Ltd. of 50% make, weave according to well-established law, make the braided wire of metric count 3/15, make the reeled yarn of weight 250g afterwards with ryce week 200cm.The reeled yarn of making is dyeed with cation dyes according to well-established law, implement suction with the suction softener and handle.Adopt the tufting machine (machine tuft) of 5/32 specification to make the long 12mm of fine hair, order is paid 800g/m 2Bath mat.To the bath mat that makes adopt staphylococcus aureus (Staphylococcus aureus ATCC6538P, logA=4.3, logB=7.1) and Escherichia coli (Escherichia coli NBRC3301, logA=4.4 logB=7.5) estimate anti-microbial property.The bath mat that makes as shown in table 6 has excellent antibiotic property.
Table 6
logC The bactericidal activity value The bacteriostatic activity value
Staphylococcus aureus 2.2 2.1 4.9
Escherichia coli 1.3 3.1 6.2
In addition, for the above-mentioned bath mat that makes, adopt 2 kinds of tinea alba bacterium to estimate fungus resistance.The bath mat that makes as shown in table 7 also produces effect to fungi.
Table 7
Tinea alba bacterial classification class Inoculation bacterium number There is not processing cloth (nylon cloth) bacterium number Viable count
Trichophyton mentagrophytes (Trichophyton menntagrophytes) NBRC 32412 1.1×10 5 1.2×10 5 Less than 200
Trichophyton rubrum (Trichophyton rubrum) NBRC 32409 1.4×10 5 8.2×10 4 Less than 200

Claims (7)

1. give the method for the antibiotic anti-fungi performance of fibrous structure thing, it is characterized in that, the acrylic fiber that contains silver-colored compounds is implemented heat treatment form the acrylic fiber that supports silver in the scope of pH1-6, with its formation fiber as the fibrous structure thing, making its content is 5-15 weight %.
2. method of giving the antibiotic anti-fungi performance of fibrous structure thing as claimed in claim 1 is characterized in that, the acrylic fiber that contains silver-colored compounds has anionic property functional group.
3. method of giving the antibiotic anti-fungi performance of fibrous structure thing as claimed in claim 1 or 2 is characterized in that, heat treatment is 100-160 ℃ damp and hot or dry heat treatment.
4. as each described method of giving the antibiotic anti-fungi performance of fibrous structure thing of claim 1-3, it is characterized in that the silver content that supports the acrylic fiber of silver is 1-100mmol/kg.
5. as each described method of giving the antibiotic anti-fungi performance of fibrous structure thing of claim 1-4, it is characterized in that the fibrous structure thing contains cotton fiber.
6. fibre, at least a portion has the fibrous structure thing of giving antibiotic anti-fungi performance with each described adding method of above-mentioned claim 1-5.
7. fibre as claimed in claim 6, it is characterized in that fibre is selected from inner lining material, pyjamas, bathing gown, towel, bath mat, carpet, felt, bedding, curtain, the chair lining cloth of undershirt, loincloth, motion body harness, mouth mask, handbag, socks, stocking, the stocking sole, footwear.
CNA2005100924640A 2005-03-10 2005-08-22 Method with antibiotic and antifungal property for fabric construction Pending CN1831232A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100395009C (en) * 2006-10-17 2008-06-18 浙江大学 Antibacterial hollow-fiber membrane, preparation method and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100395009C (en) * 2006-10-17 2008-06-18 浙江大学 Antibacterial hollow-fiber membrane, preparation method and application

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