JP2005139561A - Method for carrying out bacteriostatic processing and bacteriostatic fiber product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method capable of providing a fiber product satisfying a standard of bacteriostatic performance specified by Japan Textile Evaluation Technology Council also in a test method by bacterial transferring method of quantitative test for JIS L 1902 (2002) [antibacterial testing method of fiber products and antibacterial effect] and to provide the above fiber product. <P>SOLUTION: The method for carrying out bacteriostatic processing comprises treating a fiber product with a treating liquid containing a cationic polymer represented by formula [1] (wherein R<SP>1</SP>is a 3-10C alkylene group; R<SP>2</SP>is a 2-8C alkylene group having an ethereal oxygen atom; n is a recurring number; A<SP>-</SP>is an anion) and having 5,000-80,000 weight-average molecular weight and other aqueous resin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antibacterial processing method for fiber products and an antibacterial fiber product obtained by the processing method. More specifically, the present invention shows an antibacterial effect with washing durability in the antibacterial evaluation by the bacteria transfer method stipulated in JIS L 1902 (2002) “Antimicrobial test method / antibacterial effect of textile products”. The present invention relates to an antibacterial processing method for obtaining a fiber product and an antibacterial fiber product obtained by the processing method.

  In recent years, awareness of hygiene has increased, and many antibacterial products have been put on the market.

  Regarding textile products, the Japan Fiber Technology Evaluation Council (hereinafter abbreviated as the Textile Technology Association) has issued SEK mark certification for textile products that meet certain standards. SEK mark of antibacterial processing is issued for textile products that suppress the growth of As a test method for the antibacterial efficacy of a textile product subjected to antibacterial processing, a bacterial solution absorption method has been adopted in a quantitative test of JIS L 1902 (2002) “Antibacterial test method / antibacterial effect of textile product”. However, especially in hospitals and other medical institutions, air conditioning facilities are in place, and in applications such as nursing clothes and curtains, it is difficult to think of wet conditions such as the bacterial solution absorption method, and it is recognized that the evaluation conditions do not match the actual situation. Since November 2003, in the field of medical-related nursing clothes and curtains, the quantitative test of JIS L 1902 (2002) “Anti-bacterial test method / anti-bacterial effect of textile products” under the evaluation conditions assuming a dry state The bacteria transfer method was defined as a test method for antibacterial efficacy at the time of obtaining the SEK mark. However, since this bacteria transfer method is a method in which bacteria are once collected on a membrane filter and then transferred to a sample, the sample becomes almost dry, and the elution of the drug is much less than that of the conventional bacterial liquid absorption method. Furthermore, since the culture time of the sample to which the bacteria are transferred is as short as 4 hours, the drug is required to have an immediate effect, but it is difficult to cope with the conventional antibacterial agent alone. For example, in the case of textile products treated with silver antibacterial kneaded yarn or pyridine compounds, the immediate effect is poor, and silver, silver ions and pyridine compounds are taken into the cells and kill the bacteria Therefore, the present situation is that the antibacterial effect cannot be obtained by the bacterial transcription method in which elution cannot be expected. In addition, low-molecular-weight cationic surfactant-based antibacterial agents have a high immediate effect, so they may show antibacterial effects even in the bacteria transfer method, but they are not very durable against washing and are irritating to the skin. Due to its high cost, it is rarely used for medical applications. On the other hand, high molecular weight cationic compounds also have immediate effects, and even if they do not elute, they are said to destroy the cell wall by contact with bacteria. The current antibacterial property is poor.

  Japanese Patent Application Laid-Open No. 2001-278716 suggests that acrylic, urethane, oxazoline, and silicone resins are used in combination with a cationic polymer having antibacterial properties in order to improve washing durability ( Patent Document 1), the details thereof, and the effect of the bacterial transfer method, which is antibacterial evaluation in a dry state, are not described at all.

  For this reason, antibacterial processing methods and antibacterial fiber products exhibiting antibacterial effects are also strongly desired in the bacterial transfer method required by the Textile Technology Association.

JP 2001-278716 page 5

  The present invention can also satisfy the antibacterial performance standards defined by the Japan Science and Technology Association, even in the JIS L 1902 (2002) “Test method for antibacterial properties of textile products / Test method using antibacterial effect” by the bacterial transfer method. An object of the present invention is to provide an antibacterial processing method for obtaining a textile product and an antimicrobial fiber product obtained by the processing method.

  As a result of intensive studies in order to solve the above problems, the present inventors have treated a textile product with a treatment liquid containing a specific cationic polymer and another aqueous resin, whereby a bacterial solution absorption method and a fungus are obtained. It was found that antibacterial fiber products exhibiting good antibacterial properties can be obtained in both test methods of the transfer method, and the present invention has been completed based on this finding.

  That is, the present invention includes treating a fiber product with a treatment liquid containing a cationic polymer having a weight average molecular weight of 5,000 to 80,000 represented by the following general formula [1] and another aqueous resin. Provide a method for antibacterial processing of textile products.

Wherein R ¹ represents an alkylene group having 3 to 10 carbon atoms, R ² represents an alkylene group having 2 to 8 carbon atoms having an etheric oxygen atom, n represents a repeating number, and A ⁻ represents an anion. Represents.)
Moreover, the antibacterial processing method for a textile product of the present invention is characterized in that the other aqueous resin is at least one selected from the group consisting of an aqueous aminoplast resin, an aqueous urethane resin, an aqueous silicone resin, and an aqueous acrylic resin. It is characterized by being.

  Furthermore, this invention provides the antimicrobial fiber product obtained by the said antimicrobial processing method.

  According to the antibacterial processing method for textile products of the present invention, it is defined in JIS L 1902 (2002) “Antimicrobial test method and antibacterial effect of textile products”, which is a condition for the issuance of SEK mark certification by the Japan Textile Technology Association. In the bacterial liquid absorption method and the bacterial transcription method of the quantitative test, an antibacterial fiber product that can satisfy the evaluation standard can be obtained.

  The antibacterial processing method for a textile product of the present invention is a treatment liquid containing a cationic polymer having a weight average molecular weight of 5,000 to 80,000 represented by the above general formula [1] and another aqueous resin, and the textile product. Processing.

In the cationic polymer having a weight average molecular weight of 5,000 to 80,000 represented by the general formula [1] used in the present invention, the alkylene group having 3 to 10 carbon atoms represented by R ¹ is not particularly limited. Either a chain alkylene group or a branched alkylene group can be used. Examples of such an alkylene group include a propylene group, a trimethylene group, a butylene group, a hexamethylene group, a 2-ethylhexamethylene group, an octamethylene group, and a decamethylene group. There is no particular limitation on the C2-C8 alkylene group having an etheric oxygen atom represented by R ² , such as methyleneoxymethylene group, methyleneoxyethylene group, ethyleneoxyethylene group, ethyleneoxymethyleneoxyethylene group, etc. Can be mentioned.

The anion represented by A ⁻ is not particularly limited as long as it is an anion that forms a quaternary ammonium compound. For example, formic acid, acetic acid, propionic acid, gluconic acid, lactic acid, fumaric acid, maleic acid, adipic acid, etc. An anion derived from a monovalent or polyvalent carboxylic acid, an acidic phosphate anion, an alkyl sulfate anion, a halogen anion, a sulfate anion, a nitrate anion, and a phosphate anion. Among these anions, chlorine ions and bromine ions are particularly preferable.

  The weight average molecular weight of the cationic polymer to be used is 5,000 to 80,000, more preferably 10,000 to 40,000, and n is the number of repetitions satisfying these weight average molecular weights. When the weight average molecular weight is less than 5,000, the antibacterial property of the cationic polymer is relatively weak, and it is necessary to treat the cationic polymer at a high concentration in order to obtain sufficient antibacterial properties, which is not preferable economically. When the weight average molecular weight exceeds 80,000, the viscosity of the cationic polymer is increased, and workability may be deteriorated. The weight average molecular weight of these cationic polymers can be measured by gel permeation chromatography using polyethylene glycol having a known molecular weight as a standard substance.

  Examples of the cationic polymer represented by the general formula [1] used in the present invention include poly [oxymethylene (dimethyliminio) trimethylene (dimethyliminio) methylene dihalide] and poly [oxymethylene (dimethyliminio). Hexamethylene (dimethyliminio) methylene dihalide], poly [oxyethylene (dimethyliminio) trimethylene (dimethyliminio) ethylene dihalide], poly [oxyethylene (dimethyliminio) hexamethylene (dimethyliminio) ethylenedi Halide], poly [oxyethyleneoxymethylene (dimethyliminio) trimethylene (dimethyliminio) ethylene dihalide] and poly [oxymethyleneoxyethylene (dimethyliminio) hexamethylene (dimethyliminio) ethylene dihalide ] And the like. These cationic polymers include, for example, N, N, N ′, N′-tetramethyl-1,3-propanediamine, N, N, N ′, N′-tetramethyl-1,4-butanediamine, N, One or more tetramethyldiamines such as N, N ′, N′-tetramethyl-1,3-butanediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, and di (chloro It can be produced by reacting one or more dichloro compounds such as methyl) ether, bis (2-chloroethyl) ether, di (chloromethyl) formal, and bis (2-chloroethyl) formal.

  Preferred examples of other aqueous resins used in the method for sterilizing textile products according to the present invention include aqueous aminoplast resins, aqueous urethane resins, aqueous silicone resins, and aqueous acrylic resins.

  The aqueous aminoplast resin used in the present invention is a resin obtained by reacting an amino group-containing compound with an aldehyde compound, such as dimethylol urea, trimethylol melamine, methylated trimethylol melamine, dimethylol dihydroxyethylene urea. Dimethyldihydroxyethyleneurea, dimethylolethyleneurea, methylated dimethylolpropyleneurea, tetramethylolacetyleneurea, dimethylolalkyltriazine, dimethyloluron, methylated dimethyloluron, hexamethylolmelamine, dimethylolcarbamate and the like. These aqueous aminoplast resins can be used alone or in combination of two or more. When these aqueous aminoplast resins are used, it is preferable to use a crosslinking catalyst in combination with the treatment bath. Examples of the catalyst used include magnesium chloride, zinc chloride, zinc nitrate, and boron fluoride. Examples thereof include magnesium, zinc borofluoride, and ammonium chloride.

  Examples of the aqueous urethane resin used in the present invention include a forced emulsification type urethane resin and a self-emulsification type urethane resin. Forced emulsification type urethane resin is a urethane resin that is forcibly emulsified in water using an emulsifier such as a nonionic surfactant or an anionic surfactant. In the urethane resin structure, nonionic groups such as polyoxyethylene groups, anionic groups such as carboxyl groups, and cationic groups such as tertiary amines or quaternary ammonium salts are incorporated as water-soluble addition groups. To emulsify. The method for producing the forced emulsification type urethane resin used is not particularly limited, but for example, a polyaddition reaction is performed using a polyisocyanate compound, a polymer polyol and, if necessary, a chain extender, and an isocyanate group is formed at the terminal. A urethane prepolymer having the following is produced. At this time, in the production method of the isocyanate group-terminated urethane prepolymer, the reaction can be carried out at a temperature of 40 to 150 ° C. by a one-shot method (one-stage type) or a multi-stage isocyanate polyaddition reaction method. A reaction catalyst such as dibutyltin dilaurate, stannous octoate, dibutyltin-2-ethylhexoate, triethylamine, triethylenediamine, or N-methylmorpholine can be added. Next, a chain extender is added to carry out a chain extension reaction, and the resulting urethane resin is forcibly emulsified in water using an emulsifier such as a nonionic surfactant or an anionic surfactant to produce a forced emulsification type aqueous solution. Manufacture urethane resin. In addition, a polyaddition reaction is performed using a polyisocyanate compound, a polymer polyol and, if necessary, a chain extender to produce a urethane prepolymer having an isocyanate group at the terminal, and the remaining isocyanate group is converted to sodium bisulfite or methyl ethyl ketoxime. A blocked urethane group-containing water-based urethane resin that is blocked by the above method is also useful as the water-based urethane resin used in the present invention.

  Further, although there is no particular limitation on the method for producing the self-emulsifying urethane resin used, for example, a polyisocyanate compound, a polyol compound having a polyoxyethylene group in an amount sufficient to emulsify the resulting urethane resin is used. A polyaddition reaction is carried out using the polymer polyol to be contained and, if necessary, a chain extender to produce a urethane prepolymer having an isocyanate group at the terminal. Next, a chain extender is added to carry out a chain extension reaction, and the resulting urethane resin is emulsified in water to produce a nonionic self-emulsifying aqueous urethane resin. If a compound having an anionic hydrophilic group and at least two active hydrogens in the molecule is used instead of the polyol compound having a polyoxyethylene group used at this time, an anionic self-emulsifying aqueous urethane resin is obtained. When a compound having a cationic hydrophilic group and at least two active hydrogens in the molecule is used, a cationic self-emulsifying aqueous urethane resin can be obtained. These water-based urethane resins can be used alone or in combination of two or more.

  Examples of the polyisocyanate compound used in the production of the aqueous urethane resin used in the present invention include aliphatic diisocyanate compounds such as tramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, and trimethylhexamethylene diisocyanate, isophorone diisocyanate, Hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate, alicyclic diisocyanate compounds such as norbornane diisocyanate, lysine diisocyanate, m-phenylene diisocyanate, p -Phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate 4,4′-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate, 1,5-naphthalene Examples thereof include aromatic diisocyanates such as diisocyanate, tolidine diisocyanate, tetramethylene xylylene diisocyanate, and xylylene diisocyanate.

  Examples of the polymer polyol include polyether polyols, polyester polyols, polycarbonate polyols, etc., and polyether polyols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, bisphenol A, bisphenol S, hydrogenated bisphenol A, aconitic acid, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine Compounds having at least two active hydrogens such as pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid, 1,2,3-propanetrithiol, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran And a homopolymer obtained by addition polymerization of one or more monomers such as cyclohexylene by a conventional method, a block copolymer, and a random copolymer. Polyester polyols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6- Hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of 300 to 1000, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol Diol components such as S, hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts, dimer acid, oxalic acid, adipic acid, azelaic acid, Silic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2, By dehydration condensation reaction with dicarboxylic acid components such as 6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bisphenoxyethane-p, p′-dicarboxylic acid, dicarboxylic acid anhydride and ester-forming derivatives Examples thereof include polyester polyols obtained, polyester polyols obtained by ring-opening polymerization reaction of cyclic ester compounds such as ε-caprolactone, and polyester polyols obtained by copolymerizing these. Examples of polycarbonate polyols include 1, 4-butanegio And polycarbonate polyols obtained by reaction of glycols such as di-, 1,6-hexanediol and diethylene glycol with diphenyl carbonate and phosgene.

  Examples of the chain extender include low molecular weight polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, sorbitol, ethylenediamine, propylenediamine, Examples include hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, low molecular weight polyamines such as isophoronediamine, diethylenetriamine, and triethylenetetramine. Examples of chain extenders include water-soluble polyamines, hydrazine, and derivatives thereof. Specific examples include ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazi. , Isophorone diamine, diethylenetriamine, triethylenetetramine, amidoamine derived from diprimary amine and monocarboxylic acid, monoketimine of diprimary amine, 2 to 4 carbon atoms having at least two hydrazino groups in the molecule 1,1′-ethylenedihydrazine, 1,1′-trimethylenedihydrazine, 1,1 ′-(1,4-butylene) dihydrazine, which is an aliphatic water-soluble dihydrazine compound, having 2 to 10 carbon atoms Examples of the dicarboxylic acid dihydrazide compound include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, and itaconic acid dihydrazide.

  Examples of the compound having an anionic hydrophilic group and at least two active hydrogens in the molecule used for imparting an anionic group include 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid. Examples of the compound having a cationic hydrophilic group and at least two active hydrogens in the molecule include N-methyldimethylolamine, N-ethyldimethylolamine, N-methyldiethanolamine, and N-ethyldiethanolamine. , N-isobutyldiethanolamine and the like. It is preferable that the anionic hydrophilic group and the cationic hydrophilic group in the urethane prepolymer produced using these compounds are neutralized.

  Examples of the aqueous acrylic resin used in the present invention include glycidyl acrylate, glycidyl methacrylate, acrylamide, acrylic acid, methacrylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, dimethylaminoethylmethyl methacrylate, silicone-modified methacrylate, An aqueous acrylic resin obtained by emulsion polymerization using one or more acrylic monomers such as urethane-modified methacrylate and alkylol alkylamide alone or in combination. Further, other monomers copolymerizable with these acrylic monomers, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isopropyl acrylate, isobutyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, lauryl Acrylic ester monomers such as methacrylate and stearyl methacrylate, acrylic Examples include aqueous acrylic resins obtained by emulsifying and co-polymerizing ethylenic monomers such as nitrile, vinyl acetate, vinyl pyridine, vinyl pyrrolidone, methyl crotonate, maleic anhydride, styrene, α-methyl styrene and the like with the acrylic monomers. it can. These aqueous acrylic resins can be used alone or in combination of two or more.

  Examples of the aqueous silicone resin used in the present invention include methyl hydrogen polysiloxane, dimethyl polysiloxane, epoxy-modified polysiloxane, amino-modified polysiloxane, polyether-modified polysiloxane, carboxylic acid-modified polysiloxane, mercapto-modified polysiloxane, Examples thereof include emulsions and aqueous solutions of silanol group-containing polysiloxanes, alkoxy-modified polysiloxanes, carbinol-modified polysiloxanes, fatty acid ester-modified polysiloxanes, and alkyl-modified polysiloxanes. These aqueous silicone resins can be used alone or in combination of two or more.

  The material of the textile product used in the present invention is not particularly limited. For example, natural fibers such as cotton, hemp, wool, and silk, regenerated cellulose fibers such as rayon, cupra, and tencel (trademark), semi-finished materials such as acetate and promix, etc. Examples thereof include synthetic fibers such as synthetic fibers, polyamide fibers, polyester fibers, acrylic fibers, polyolefin fibers, polyvinyl chloride fibers, polyurethane fibers, polyimide fibers, and composite fibers of these fibers. The form of the fiber product is not particularly limited, and examples thereof include short fibers, long fibers, yarns, woven fabrics, knitted fabrics, non-woven fabrics, and papers.

  There is no restriction | limiting in particular in the method to process the textiles of this invention, According to the form or kind of textiles, it can select suitably, For example, a padding process, a dipping process, a spray process etc. can be mentioned. The amount of the cationic polymer of the general formula [1] applied to the fiber product is 0.05 to 5% by mass, preferably 0.1 to 3% by mass, particularly 0.3 to 2%, based on the fiber product. It is preferable that it is mass%. Moreover, 10-2000 mass parts is preferable with respect to 100 mass parts of cationic polymer of the said General formula [1], and, as for the application amount of the said other aqueous resin, 50-1000 are especially preferable. And the antibacterial fiber product which provided wash resistance by adding heat processing with respect to the fiber product which provided the cationic polymer and other aqueous resin is obtained, As heat processing temperature at this time, it is 100- 250 degreeC is preferable and it is especially preferable that it is 120-200 degreeC.

  EXAMPLES Hereinafter, although an Example is given and this invention is further demonstrated, this invention is not restrict | limited at all by these Examples.

  In Examples and Comparative Examples, the following chemicals were blended with water at the blending ratios (mass%) shown in Table 1 and processed into test cloths (broad cloths of cotton / polyester (50/50) blends).

Cationic polymer A: 50 mass% aqueous solution of poly [oxyethylene (dimethyliminio) propyl (dimethyliminio) ethylene dihalide] having a weight average molecular weight of 25000 Cationic polymer B: poly [oxyethylene (dimethyl) having a weight average molecular weight of 10,000 Imminio) propyl (dimethyliminio) ethylene dihalide] 50 mass% aqueous solution Cationic polymer C: 50 mass of poly [oxyethylene (dimethyliminio) propyl (dimethyliminio) ethylene dihalide] having a weight average molecular weight of 40,000 % Aqueous solution Comparative antibacterial agent A: 50% by weight dispersion of zinc pyrithione Aqueous aminoplast resin: 50% by weight aqueous solution of dimethylol dihydroxyethylene urea Catalyst for aqueous aminoplast resin: 50% aqueous solution of magnesium hydrochloride Aqueous urea Emissions-based resin: Ebafanoru AL-3 (Nicca Chemical Co., bisulfite blocked isocyanate group-containing urethane resin emulsion)
Catalyst for water-based urethane resin: NK Catalyst TF (Nikka Chemical Co., Ltd., amine compound)
Aqueous acrylic resin: Toaclon XA-2291D (Toagosei Co., Ltd.)
Aqueous silicone resin: Drypon 600 (Nikka Chemical Co., Ltd., methyl hydrogen polysiloxane emulsion)
Catalyst for aqueous silicone resin: Drypon Z-7 (Nikka Chemical Co., Ltd., zinc catalyst)
The antibacterial property of the antibacterial fiber product was evaluated by the bacterial solution absorption method and the bacterial transcription method of the quantitative test of JIS L 1902 (2002) “Antibacterial test method / antibacterial effect of fiber product”.

Test bacteria:
Staphylococcus aureus ATCC 6538P
Klebsiella pneumoniae ATCC 4352
The criteria for antibacterial activity of the Japan Federation of Technical Sciences are as follows.

  When the evaluation method is the bacterial solution absorption method, the common logarithm of the number of viable bacteria after the 18-hour culture test of the antibacterial processed sample is obtained from the common logarithm of the number of viable bacteria immediately after inoculation with the test cloth on the standard cloth. The subtracted value is set as the bactericidal activity value, and when the bactericidal activity value is larger than 0, it is determined that there is an effect. This is performed for both the samples before and after washing to determine the washing durability.

  In addition, in the case of the bacterial transfer method, from the common logarithm of the number of viable cells after a 4-hour culture test at 20 ° C. of a standard cloth, the number of viable cells after a 4-hour culture test at 20 ° C. of a bactericidal processed sample A value obtained by subtracting the logarithmic value is used as a bacteria reduction value. When the bacteria reduction value is larger than 0.5, it is determined that the effect is effective. This is performed for both the samples before and after washing to determine the washing durability.

  Washing was performed 50 times in accordance with the washing method defined by the Japan Textile Technology Association. The washing method was to wash the antibacterial fiber product under conditions of 120 mL of JAFET standard detergent / 90 L of water and 1:30 bath ratio at 80 ° C. for 120 minutes, dehydrated, and then rinse with running water for 15 minutes twice. . Assuming that this operation corresponds to 10 washings, the operation was repeated a total of 5 times (50 washings) and air-dried.

Example 1
The test cloth was dipped in a padding bath of 4 g of cationic polymer A, 5 g of aqueous aminoplast resin, 1 g of catalyst for aqueous aminoplast resin, and 90 g of water to obtain a 70% pick-up with a mangle (amount of cationic polymer A with respect to fabric 1. (4% by mass, amount of aqueous aminoplast resin 1.7% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial properties of the resulting antimicrobial fiber product were evaluated.

As for the evaluation with Staphylococcus aureus by the mycobacterial absorption method, before washing (L-0), the number of viable bacteria immediately after inoculation of the test bacteria on the standard cloth is 8.0 × 10 ⁴ , and the antimicrobial fiber product Since the number of viable bacteria after the 18-hour culture test at 38 ° C. was less than 20, its bactericidal activity value was larger than 3.6. Even after 50 launderings (L-50), the number of viable bacteria after the 18-hour culture test at 38 ° C. of the antibacterial fiber product was less than 20, so the bactericidal activity value was greater than 3.6. became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial solution absorption method, the number of viable bacteria immediately after inoculation of the test cloth of the standard cloth was 4.0 × 10 ⁴ before washing, and the antibacterial fiber product was 18 at 38 ° C. Since the number of viable bacteria after the time culture test was less than 20, the bactericidal activity value was larger than 3.3. Even after 50 washings, the number of viable bacteria after the 18-hour culture test at 38 ° C. of the antimicrobial fiber product was less than 20, so the bactericidal activity value was larger than 3.3.

As for the evaluation with Staphylococcus aureus by the bacterial transfer method, before washing (L-0), the number of viable cells after the culture test at 20 ° C. for 4 hours at 1.6 ° C. is 1.6 × 10 ^6. Since the number of viable bacteria after the culture test at 20 ° C. for 4 hours was less than 20, the bacterial reduction value was larger than 4.8. Even after 50 washings (L-50), the number of viable bacteria after the 4-hour culture test at 20 ° C. of the antibacterial fiber product was less than 20, so that the bacteria reduction value was greater than 4.8. became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the number of viable bacteria after culturing for 4 hours at 20 ° C. of the standard cloth was 5.6 × 10 ⁵ before washing (L-0). Since the number of viable bacteria after the culture test at 20 ° C. for 4 hours was less than 20, the bacterial reduction value was larger than 4.4. Even after 50 launderings (L-50), the number of viable bacteria after the 4-hour culture test at 20 ° C. of the antibacterial fiber product was less than 20, so that the bacteria reduction value was greater than 4.4. became.

Example 2
The test cloth was dipped in a padding bath of 4 g of cationic polymer B, 5 g of aqueous aminoplast resin, 1 g of catalyst for aqueous aminoplast resin and 90 g of water, and squeezed with a mangle to make a pickup 70% (amount of cationic polymer B with respect to fabric 1. (4% by mass, amount of aqueous aminoplast resin 1.7% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial properties of the resulting antimicrobial fiber product were evaluated.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value was 3 after 50 washings (L-50). It was greater than 3.

  The evaluation with Staphylococcus aureus by the bacteria transfer method shows that the bacteria reduction value is larger than 4.8 before washing (L-0), and the bacteria reduction value is 3.2 after 50 washings (L-50). It became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value is larger than 4.4 before washing (L-0), and the bacterial reduction value is 3.0 after 50 washings (L-50). It became.

Example 3
The test cloth was dipped in a padding bath of 4 g of cationic polymer C, 5 g of aqueous aminoplast resin, 1 g of catalyst for aqueous aminoplast resin and 90 g of water, and squeezed with a mangle to make a pickup 70% (amount of cationic polymer C relative to the fabric 1. (4% by mass, amount of aqueous aminoplast resin 1.7% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial properties of the resulting antimicrobial fiber product were evaluated.

  Evaluation with Staphylococcus aureus by bacterial liquid absorption method, before washing (L-0), the bactericidal activity value is greater than 3.6, and after 50 washings (L-50) the bactericidal activity value is 3.6. It became bigger. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value was 3 after 50 washings (L-50). It was greater than 3.

  The evaluation with Staphylococcus aureus by the bacteria transfer method shows that the bacteria reduction value is larger than 4.8 before washing (L-0), and the bacteria reduction value is 4.8 even after 50 washings (L-50). It became bigger. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value is larger than 4.4 before washing (L-0), and the bacterial reduction value is 4.4 even after 50 washings (L-50). It became bigger.

Example 4
The test cloth was dipped in a padding bath of 4 g of cationic polymer A, 5 g of water-based urethane resin, 1 g of catalyst for water-based urethane resin and 90 g of water, and squeezed with a mangle to make 70% pickup (amount of cationic polymer A with respect to the cloth was 1.4 mass). %, Amount of water-based urethane resin 1.0 mass%) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial properties of the resulting antimicrobial fiber product were evaluated.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value was 3 after 50 washings (L-50). It was greater than 3.

  The evaluation with Staphylococcus aureus by the bacteria transfer method shows that the bacteria reduction value is larger than 4.8 before washing (L-0), and the bacteria reduction value is 2.2 after 50 washings (L-50). It became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacteria reduction value was larger than 4.4 before washing (L-0), and the bacteria reduction value after washing 50 times (L-50) was 1.9. It became.

Example 5
The test cloth was dipped in a padding bath of 4 g of cationic polymer B, 5 g of aqueous urethane resin, 1 g of catalyst for aqueous urethane resin and 90 g of water, and squeezed with a mangle to make a pickup 70% (amount of cationic polymer B with respect to the cloth was 1.4 mass). %, Amount of water-based urethane resin 1.0 mass%) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial properties of the resulting antimicrobial fiber product were evaluated.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. Moreover, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value after washing 50 times (L-50) was 3. 0.

  As for the evaluation with Staphylococcus aureus by the bacterial transfer method, the bacterial reduction value is larger than 4.8 before washing (L-0), and the bacterial reduction value is 1.3 after 50 washings (L-50). It became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value is larger than 4.4 before washing (L-0), and the bacterial reduction value is 1.0 after 50 washings (L-50). It became.

Example 6
The test cloth was dipped in a padding bath of 4 g of cationic polymer C, 5 g of aqueous urethane resin, 1 g of catalyst for aqueous urethane resin, and 90 g of water to obtain a 70% pick-up with mangle (amount of cationic polymer C with respect to the cloth was 1.4 mass). %, Amount of water-based urethane resin 1.0 mass%) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial properties of the resulting antimicrobial fiber product were evaluated.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value was 3 after 50 washings (L-50). It was greater than 3.

  As for the evaluation with Staphylococcus aureus by the bacterial transfer method, the bacterial reduction value is larger than 4.8 before washing (L-0), and the bacterial reduction value is 2.4 after 50 washings (L-50). It became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value is larger than 4.4 before washing (L-0), and the bacterial reduction value is 2.1 after 50 washings (L-50). It became.

Example 7
The test cloth was dipped in a padding bath of 4 g of cationic polymer A, 5 g of aqueous acrylic resin, and 91 g of water, and squeezed with a mangle to make a pickup of 70% (amount of cationic polymer A with respect to the cloth was 1.4% by mass, amount of aqueous acrylic resin) 1.7% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial fiber product thus obtained was evaluated for antibacterial properties.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value was 3 after 50 washings (L-50). It was greater than 3.

  The evaluation with Staphylococcus aureus by the bacteria transfer method shows that the bacteria reduction value is larger than 4.8 before washing (L-0), and the bacteria reduction value is 2.0 after 50 washings (L-50). It became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacteria reduction value is larger than 4.4 before washing (L-0), and the bacteria reduction value is 1.8 after washing 50 times (L-50). It became.

Example 8
The test cloth was dipped in a padding bath of 4 g of cationic polymer B, 5 g of aqueous acrylic resin, and 91 g of water, and was squeezed with a mangle to make a pickup 70% (1.4% by mass of cationic polymer B relative to the fabric, the amount of aqueous acrylic resin) 1.7% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial fiber product thus obtained was evaluated for antibacterial properties.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. Moreover, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value after washing 50 times (L-50) was 2. Nine.

  The evaluation with Staphylococcus aureus by the bacteria transfer method shows that the bacteria reduction value is larger than 4.8 before washing (L-0), and the bacteria reduction value is 1.2 after 50 washings (L-50). It became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value is larger than 4.4 before washing (L-0), and the bacterial reduction value is 0.9 after 50 washings (L-50). It became.

Example 9
The test cloth was dipped in a padding bath of 4 g of cationic polymer C, 5 g of aqueous acrylic resin and 91 g of water, and was squeezed with a mangle to make a pickup of 70% (1.4% by mass of cationic polymer C relative to the fabric, the amount of aqueous acrylic resin) 1.7% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial fiber product thus obtained was evaluated for antibacterial properties.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value was 3 after 50 washings (L-50). It was greater than 3.

  As for the evaluation with Staphylococcus aureus by the bacteria transfer method, the bacteria reduction value is larger than 4.8 before washing (L-0), and the bacteria reduction value is 2.3 after 50 washings (L-50). It became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value was larger than 4.4 before washing (L-0), and the bacterial reduction value was 2.0 after 50 washings (L-50). It became.

Example 10
The test cloth was dipped in a padding bath of 4 g of cationic polymer A, 5 g of aqueous silicone resin, 1 g of catalyst for aqueous silicone resin and 90 g of water, and squeezed with a mangle to make a pickup 70% (amount of cationic polymer A with respect to the cloth was 1.4 mass). %, Amount of aqueous silicone resin 1.9% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial properties of the resulting antimicrobial fiber product were evaluated.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value was 3 after 50 washings (L-50). It was greater than 3.

  As for the evaluation with Staphylococcus aureus by the bacterial transfer method, the bacterial reduction value is larger than 4.8 before washing (L-0), and the bacterial reduction value is 2.1 after 50 washings (L-50). It became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacteria reduction value was larger than 4.4 before washing (L-0), and the bacteria reduction value after washing 50 times (L-50) was 1.9. It became.

Example 11
The test cloth was dipped in a padding bath of 4 g of cationic polymer B, 5 g of aqueous silicone resin, 1 g of catalyst for aqueous silicone resin and 90 g of water, and squeezed with a mangle to obtain a pickup of 70% (amount of cationic polymer B with respect to the cloth was 1.4 mass). %, Amount of aqueous silicone resin 1.9% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial properties of the resulting antimicrobial fiber product were evaluated.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. Moreover, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value after washing 50 times (L-50) was 2. Nine.

  As for the evaluation with Staphylococcus aureus by the bacterial transfer method, the bacterial reduction value is larger than 4.8 before washing (L-0), and the bacterial reduction value is 1.3 after 50 washings (L-50). It became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value is larger than 4.4 before washing (L-0), and the bacterial reduction value is 0.9 after 50 washings (L-50). It became.

Example 12
The test cloth was dipped in a padding bath of 4 g of cationic polymer C, 5 g of aqueous silicone resin, 1 g of catalyst for aqueous silicone resin and 90 g of water, and squeezed with a mangle to make a pickup 70% (amount of cationic polymer C with respect to the cloth was 1.4 mass). %, Amount of aqueous silicone resin 1.9% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial properties of the resulting antimicrobial fiber product were evaluated.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value was 3 after 50 washings (L-50). It was greater than 3.

  The evaluation with Staphylococcus aureus by the bacteria transfer method shows that the bacteria reduction value is larger than 4.8 before washing (L-0), and the bacteria reduction value is 2.3 after 50 washings (L-50). It became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value is larger than 4.4 before washing (L-0), and the bacterial reduction value is 2.1 after 50 washings (L-50). It became.

Example 13
A treatment liquid prepared by mixing 6 g of cationic polymer A, 8 g of aqueous amino plus and 8 g of resin, 1.5 g of catalyst for aqueous amino plast resin and 84.5 of water was spray-treated on the test cloth (cation polymer on the dough). The amount of A is 1.5% by mass and the amount of the aqueous aminoplast resin is 2.0% by mass. After the dough is dried, it is heated at 150 ° C. for 2 minutes. .

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value was 3 after 50 washings (L-50). It was greater than 3.

  The evaluation with Staphylococcus aureus by the bacteria transfer method shows that the bacteria reduction value is larger than 4.8 before washing (L-0), and the bacteria reduction value is 4.8 even after 50 washings (L-50). It became bigger. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value is larger than 4.4 before washing (L-0), and the bacterial reduction value is 4.4 even after 50 washings (L-50). It became bigger.

Example 14
A treatment liquid prepared by mixing 6 g of the cationic polymer A, 8 g of the aqueous urethane resin, 1.5 g of the catalyst for the aqueous urethane resin and 84.5 water was sprayed on the test cloth by 50% by mass (the amount of the cationic polymer A relative to the fabric). 1.5% by mass, amount of water-based urethane resin 1.1% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and antibacterial properties were evaluated for the resulting antimicrobial fiber product.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value was 3 after 50 washings (L-50). It was greater than 3.

  As for the evaluation with Staphylococcus aureus by the bacterial transfer method, the bacterial reduction value is larger than 4.8 before washing (L-0), and the bacterial reduction value is 2.4 after 50 washings (L-50). It became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value is larger than 4.4 before washing (L-0), and the bacterial reduction value is 2.1 after 50 washings (L-50). It became.

Example 15
A treatment liquid in which 6 g of the cationic polymer A, 8 g of the aqueous acrylic resin and 86 of water were mixed was sprayed on the test cloth by 50% by mass (the amount of the cationic polymer A to the fabric was 1.5% by mass, the amount of the aqueous acrylic resin). 2.0% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial fiber product thus obtained was evaluated for antibacterial properties.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value was 3 after 50 washings (L-50). It was greater than 3.

  The evaluation with Staphylococcus aureus by the bacteria transfer method shows that the bacteria reduction value is larger than 4.8 before washing (L-0), and the bacteria reduction value is 2.2 after 50 washings (L-50). It became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value was larger than 4.4 before washing (L-0), and the bacterial reduction value was 2.0 after 50 washings (L-50). It became.

Example 16
A treatment liquid prepared by mixing 6 g of the cationic polymer A, 8 g of the aqueous silicone resin, 1.5 g of the catalyst for the aqueous silicone resin and 84.5 water was sprayed on the test cloth by 50% by mass (the amount of the cationic polymer A relative to the fabric). 1.5% by mass, amount of aqueous silicone resin 2.2% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and antibacterial properties were evaluated for the resulting antimicrobial fiber product.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value was 3 after 50 washings (L-50). It was greater than 3.

  As for the evaluation with Staphylococcus aureus by the bacteria transfer method, the bacteria reduction value is larger than 4.8 before washing (L-0), and the bacteria reduction value is 2.3 after 50 washings (L-50). It became. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value is larger than 4.4 before washing (L-0), and the bacterial reduction value is 2.1 after 50 washings (L-50). It became.

Comparative Example 1
The test cloth was dipped in a padding bath of 4 g of cationic polymer A and 96 g of water, and squeezed with a mangle to make a pickup 70% (amount of cationic polymer A with respect to the cloth was 1.4% by mass). After drying the dough, heat treatment was performed at 150 ° C. for 2 minutes. The antibacterial properties of the antibacterial fiber products obtained were evaluated.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value was 3 after 50 washings (L-50). It was greater than 3.

  The evaluation with Staphylococcus aureus by the bacteria transfer method showed that the bacteria reduction value was larger than 4.8 before washing (L-0), but the bacteria reduction value after 50 washings (L-50) was It was 0.2. In addition, the evaluation with Klebsiella pneumoniae by the bacterial transfer method showed that the bacterial reduction value was larger than 4.4 before washing (L-0), but the bacterial reduction value after 50 washings (L-50) was -0.1.

Comparative Example 2
The test cloth is dipped in a padding bath of 4 g of comparative antibacterial agent A and 96 g of water, and the pick-up is made 70% with a mangle (the amount of antibacterial component is 1.4% by mass with respect to the dough). The antibacterial properties of the antibacterial fiber products obtained were evaluated.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is higher than 3.6 before washing (L-0), and the bactericidal activity value after washing 50 times (L-50) is 1. It was eight. Moreover, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value after washing 50 times (L-50) was 0. It became 5.

  The evaluation with Staphylococcus aureus by the bacteria transfer method showed that the bacteria reduction value was 0.7 before washing (L-0) and the bacteria reduction value was -1.0 after 50 washings (L-50). It was. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value was 0.5 before washing (L-0), and the bacterial reduction value was -0.8 after 50 washings (L-50). It was.

Comparative Example 3
The test cloth was dipped in a padding bath of 4 g of comparative antibacterial agent A, 5 g of aqueous aminoplast resin, 1 g of catalyst for aqueous aminoplast resin and 90 g of water, and squeezed with a mangle to make 70% pick-up (amount of antibacterial component to fabric 1. (4% by mass, amount of aqueous aminoplast resin 1.7% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial properties of the resulting antimicrobial fiber product were evaluated.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value is 3 after 50 washings (L-50). It was larger than 6. In addition, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value was 3 after 50 washings (L-50). It was greater than 3.

  As for the evaluation with Staphylococcus aureus by the bacteria transfer method, the bacteria reduction value was 0.8 before washing (L-0), and the bacteria reduction value was 0.1 after 50 washings (L-50). . Moreover, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value was 0.7 before washing (L-0), and the bacterial reduction value was 0.1 after 50 washings (L-50). .

Comparative Example 4
The test cloth was dipped in a padding bath of 4 g of comparative antibacterial agent A, 5 g of water-based urethane resin, 1 g of catalyst for water-based urethane resin, and 90 g of water to make a squeeze pickup 70% with a mangle (amount of antibacterial component to fabric is 1.4 mass) %, Amount of water-based urethane resin 1.0 mass%) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial properties of the resulting antimicrobial fiber product were evaluated.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value after washing 50 times (L-50) is 2. It became 5. Moreover, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value after washing 50 times (L-50) was 1. Nine.

  The evaluation with Staphylococcus aureus by the bacteria transfer method showed that the bacteria reduction value was 0.7 before washing (L-0), and the bacteria reduction value was -0.2 after 50 washings (L-50). It was. Moreover, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value was 0.4 before washing (L-0), and the bacterial reduction value was -0.8 after 50 washings (L-50). there were.

Comparative Example 5
The test cloth was dipped in a padding bath of 4 g of comparative antibacterial agent A, 5 g of water-based acrylic resin and 91 g of water, and squeezed with a mangle to make 70% pick-up (1.4% by weight of antibacterial component relative to fabric, amount of water-based acrylic resin) 1.7% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial fiber product thus obtained was evaluated for antibacterial properties.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value after washing 50 times (L-50) is 2. It became four. Moreover, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value after washing 50 times (L-50) was 2. 0.

  The evaluation with Staphylococcus aureus by the bacteria transfer method showed that the bacteria reduction value was 0.7 before washing (L-0), and the bacteria reduction value was -0.5 after 50 washings (L-50). It was. Moreover, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value was 0.4 before washing (L-0), and the bacterial reduction value was -0.8 after 50 washings (L-50). there were.

Comparative Example 6
The test cloth was dipped in a padding bath of 4 g of comparative antibacterial agent A, 5 g of aqueous silicone resin, 1 g of catalyst for aqueous silicone resin, and 90 g of water to make a squeeze pickup 70% with a mangle (amount of antibacterial component to fabric is 1.4 mass) %, Amount of aqueous silicone resin 1.9% by mass) After the dough was dried, it was heat-treated at 150 ° C. for 2 minutes, and the antibacterial properties of the resulting antimicrobial fiber product were evaluated.

  As for the evaluation with Staphylococcus aureus by the bacterial liquid absorption method, the bactericidal activity value is larger than 3.6 before washing (L-0), and the bactericidal activity value after washing 50 times (L-50) is 2. It became 5. Moreover, as for the evaluation with Klebsiella pneumoniae by the bacterial liquid absorption method, the bactericidal activity value was larger than 3.3 before washing (L-0), and the bactericidal activity value after washing 50 times (L-50) was 2. It became 1.

  The evaluation with Staphylococcus aureus by the bacteria transfer method showed that the bacteria reduction value was 0.6 before washing (L-0) and the bacteria reduction value was -1.1 after 50 washings (L-50). It was. Moreover, as for the evaluation with Klebsiella pneumoniae by the bacterial transfer method, the bacterial reduction value was 0.3 before washing (L-0), and the bacterial reduction value was -0.8 after 50 washings (L-50). there were.

  The above results are summarized in Tables 1 to 4 below.

  In the examples of the present invention, before and after washing (L-0) and after washing (L-50), the antibacterial evaluation criteria of the Sengikyo Co., Ltd. using both the bacterial liquid absorption method and the bacterial transfer method. Passed. On the other hand, in Comparative Examples 1-6, in the evaluation of the bacterial liquid absorption method, both before washing (L-0) and after washing (L-50) pass the antibacterial evaluation criteria of the Sengikyo. However, in the evaluation of the bacterial transfer method, none of them reached the antibacterial evaluation standard of the Sengikyo after washing (L-50). In Comparative Examples 4, 5, and 6, in particular, in the evaluation of the bacterial transfer method using Klebsiella pneumoniae, even before washing (L-0), the antibacterial evaluation standard of Sengikyo was not reached.

  The antibacterial fiber product according to the present invention has the antibacterial effect of either the bacterial liquid absorption method or the bacterial transfer method in the durability test for washing at 80 ° C., which is required for the antibacterial processing of specific applications. It is a textile product showing good antibacterial efficacy even in evaluation. Therefore, it is possible to expand the use to care clothes and curtains of medical institutions such as hospitals that have air conditioning facilities and are in a dry state.

Claims (5)

Antibacterial processing of textile products including treating textile products with a treatment liquid containing a cationic polymer having a weight average molecular weight of 5,000 to 80,000 represented by the following general formula [1] and another aqueous resin Method.

Wherein R ¹ represents an alkylene group having 3 to 10 carbon atoms, R ² represents an alkylene group having 2 to 8 carbon atoms having an etheric oxygen atom, n represents a repeating number, and A ⁻ represents an anion. Represents.)   The antibacterial processing method according to claim 1, wherein the other aqueous resin is at least one selected from the group consisting of an aqueous aminoplast resin, an aqueous urethane resin, an aqueous silicone resin, and an aqueous acrylic resin.   The antibacterial processing method according to claim 1, comprising treating the fiber product with the treatment liquid and then performing a heat treatment at 100 to 250 ° C. at normal pressure.   An antibacterial fiber product obtained by the antibacterial processing method according to any one of claims 1 to 3. The antibacterial fiber product according to claim 4, wherein the bacterial depletion value by the bacterial transcription method stipulated in JIS L 1902 (2002) “Antimicrobial test method and antibacterial effect of textile product” is 0.5 or more.