Washing method

Abstract

To provide washing methods that can enhance the amount of phenolic antibacterial compounds with antibacterial effects remaining in fiber products.SOLUTION: The present invention provides a washing method for washing a fiber product and rinsing the fiber product after washing. The fiber product subjected to rinsing contains (a) a phenolic antibacterial compound [component (a)]. The rinsing is performed by bringing a rinse solution with a pH of 6.5 or less, containing water, into contact with the fiber product.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a washing method. [Background technology]

[0002] Regarding the washing of textile products, for example, washing and rinsing using an aqueous medium are known. In recent years, due to the increasing awareness of hygiene among consumers, there has been an increasing interest in keeping things around us clean. In particular, textile products around the kitchen, such as clothing, linens, and dishcloths, may affect the human body if bacteria are attached to them, so it is desirable to sterilize, disinfect, and treat antibacterial properties of textile products. In addition, with the spread of information linking unpleasant odors to the proliferation of microorganisms, there has been an increasing interest in removing odors by sterilizing, disinfecting, and treating antibacterial properties of textile products. As a means for suppressing the proliferation of bacteria attached to textile products such as clothing, it is known to use quaternary ammonium surfactants, phenolic antibacterial agents, biguanide compounds, and the like. In addition, aromatic chlorine compounds such as diclosan are also known as compounds having antibacterial and bactericidal properties. These compounds can be applied, for example, to detergents when washing textile products.

[0003] For example, Patent Document 1 discloses a liquid detergent composition for clothing that contains component (A): a hydroxycarboxylic acid, component (B): (b-1) a specific quaternary ammonium salt, (b-2) at least one antibacterial agent selected from the group consisting of phenolic antibacterial agents and (b-3) biguanide compounds, and component (C): a nonionic surfactant, in which the content of component (A) is 5 mass% or more relative to the total mass of the liquid detergent composition for clothing and the pH at 25°C is 2 to 6.

[0004] Patent Document 2 also describes a method for cleaning a fabric comprising the steps of: a) contacting a fabric with an aqueous cleaning solution containing at least one detersive surfactant, the aqueous cleaning solution being characterized by a first pH in the range of 7.0 to 9.0; b) increasing the pH of the aqueous cleaning solution to a second pH in the range of 10.0 to 13.0, while continuing to contact the fabric with such aqueous cleaning solution for a duration in the range of 5 minutes to 30 minutes; and c) contacting the fabric with an aqueous cleaning solution characterized by a third pH in the range of 3.0 to 6.0. and contacting the fabric with a rinse liquor, further comprising a step (b1) after step (b) and before step (c) of lowering the pH of the aqueous wash liquor back to a fourth pH in the range of 7.0 to 9.0, wherein in step (b1), the fabric is contacted with the aqueous wash liquor for a duration in the range of 1 minute to 60 minutes, and further disclosed that 5-chloro-2-(4-chlorophenoxy)phenol can be dispensed into the aqueous rinse liquor during step (c). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2018-188641 A [Patent Document 2] Special Publication No. 2022-511731 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention provides a washing method capable of increasing the amount of a phenolic antibacterial compound having an antibacterial effect remaining on a textile product. [Means for solving the problem]

[0007] The present invention relates to a washing method for washing a textile product and rinsing the washed textile product, The textile product to be rinsed contains (a) a phenolic antibacterial compound (hereinafter referred to as component (a)); Rinsing is performed by contacting the textile product with a rinsing liquid containing water and having a pH of 6.5 or less. Regarding washing method. Effect of the Invention

[0008] According to the present invention, there is provided a washing method capable of increasing the amount of a phenolic antibacterial compound having an antibacterial effect remaining on a textile product. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] In the washing method of the present invention, washing of textile products and rinsing of the washed textile products are carried out under predetermined conditions. The textile products can be washed according to known washing methods. For example, the textile products can be washed by contacting them with a cleaning solution prepared from a cleaning agent containing a surfactant, a builder, etc. More specifically, for example, a method of mixing a detergent containing a surfactant, builder, etc., with a textile product and water, and preferably applying an external force to the textile product to wash it can be mentioned. Alternatively, the detergent can be brought into contact with the textile product by a method such as immersing the textile product in a cleaning liquid in which the detergent is dissolved in water in advance, or directly applying the detergent to the textile product, and then leaving it for a certain period of time, and then performing normal washing. Washing, preferably washing with application of an external force, is usually carried out once. The method of applying an external force to the textile product may be, for example, a method of applying mechanical force using a washing machine, or a method of hand washing such as rubbing, pressing, beating, grabbing, pinching, or shaking. Usually, the laundry process includes a rinsing process after the washing process. In general, the rinsing process is carried out by supplying a liquid medium not containing a detergent, preferably water, and preferably applying an external force to the textile product to remove detergent components such as surfactants remaining on the textile product. The liquid medium used for rinsing may contain a fabric softener. In the present invention, rinsing can be carried out in accordance with a known rinsing method, except that a rinsing liquid having a pH of 6.5 or less is used. The rinsing process may be carried out once or twice or more. In the present invention, unless otherwise specified, the term "fiber retention" means an improvement in the retention of the phenolic antibacterial compound of component (a) on fibers.

[0010] The detergent and cleaning solution used for cleaning may contain components known to be used in applications such as detergents or softeners for textile products, for example, the following components (1) to (16), within the range that does not affect the effects of the present invention. The components used in the detergent and cleaning solution may be mixed into the rinsing solution within the range that does not affect the effects of the present invention.

[0011] (1) Surfactants From the viewpoint of fiber retention, the surfactant is not particularly limited, but may be one or more selected from (1-1) anionic surfactants (hereinafter also referred to as (1-1) component), (1-2) cationic surfactants (hereinafter also referred to as (1-2) component), (1-3) nonionic surfactants (hereinafter also referred to as (1-3) component), and (1-4) amphoteric surfactants (hereinafter also referred to as (1-4) component). In the present invention, the surfactants may be used alone or in combination of two or more.

[0012] Examples of the anionic surfactant of the component (1-1), from the viewpoint of fiber residue, include one or more selected from alkyl sulfates, alkenyl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, alkylbenzenesulfonic acids, alkenylbenzenesulfonic acids, alkanesulfonic acids, α-olefinsulfonic acids, internal olefinsulfonic acids, alkyl or dialkyl sulfosuccinic acids, alkenyl or dialkenyl sulfosuccinic acids, polyoxyalkylene alkyl or polyoxyalkylene dialkyl sulfosuccinic acids, polyoxyalkylene alkyl or polyoxyalkylene dialkyl sulfosuccinic acids, alkyl succinic acids, alkenyl succinic acids, fatty acids, and salts thereof. From the viewpoint of fiber retention, the salt of the anionic surfactant is preferably an alkali metal salt such as a sodium salt or a potassium salt.

[0013] From the viewpoint of fiber retention, examples of the cationic surfactant of the component (1-2) include compounds represented by the following general formula.

[0014] [ka]

[0015] [In the formula, R 1a is a chain hydrocarbon group having 8 to 24 carbon atoms, R 2a is a chain hydrocarbon group having 8 to 24 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, R 3a and R 4a are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X- is an alkyl sulfate ion having 1 to 3 carbon atoms or a halide ion.

[0016] In the above general formula, R 1a From the viewpoint of fiber retention, the carbon number of the chain hydrocarbon group is preferably 9 or more, more preferably 10 or more, and is preferably 18 or less, more preferably 14 or less, and even more preferably 12 or less.

[0017] R 2a is a chain hydrocarbon group having 8 to 24 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, R 2a From the viewpoint of fiber retention, the carbon number of the chain hydrocarbon group is preferably 9 or more, more preferably 10 or more, and is preferably 18 or less, more preferably 14 or less, and even more preferably 12 or less. R 2a From the viewpoint of fiber retention, the chain hydrocarbon group is preferably an alkyl group or an alkenyl group, more preferably an alkyl group.

[0018] R 3a , R 4aare each independently an alkyl group having 1 to 3 carbon atoms, such as a methyl group or an ethyl group, or a hydroxyalkyl group having 1 to 3 carbon atoms.

[0019] R 1a , R 2a Specific examples of the chain hydrocarbon group are octyl, nonyl, decyl, dodecyl, tetradecyl and hexadecyl groups, and from the viewpoint of fiber retention, nonyl and decyl groups are preferred, with decyl group being more preferred.

[0020] Specific examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group. - is CH3SO4 - , CH3CH2SO4 - , or a halide ion.

[0021] More specific examples of the compound represented by the above general formula, from the viewpoint of fiber retention, include one or more compounds selected from N-ethyl-N,N-dimethyltetradecyl ammonium salt, trimethylhexadecyl ammonium salt, N,N-dioctyl-N,N-dimethyl ammonium salt, N,N-dinonyl-N,N-dimethyl ammonium salt, N,N-didecyl-N,N-dimethyl ammonium salt, N,N-dioctyl-N-ethyl-N-methyl ammonium salt, N,N-dinonyl-N-ethyl-N-methyl ammonium salt, and N,N-didecyl-N-ethyl-N-methyl ammonium salt. Mono-long chain ammonium salts and di-long chain ammonium salts can also be used in combination. The counter ion of these salts is CH3SO4 - , CH3CH2SO4 - , or a halide ion such as chloride ion.

[0022] From the viewpoint of fiber retention, the cationic surfactant of the component (1-2) also includes a bispyridinium compound. Examples of bispyridinium compounds include those described in British Patent No. 1533952, Japanese Patent Publication No. 52-105228, and International Publication No. 2014 / 100807. Specifically, from the viewpoint of fiber retention, the bispyridinium compound is preferably a compound represented by the following general formula (1) or a compound represented by the following general formula (2).

[0023] [ka]

[0024] [wherein Y is an alkylene or alkenylene group having 4 to 18 carbon atoms; R 1b each represents an alkyl group having 6 to 18 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or a phenyl group with or without halogen substitution, and A is an anion. q is 1 or 2, r is 1 or 2, and q×r=2.

[0025] A is a monovalent or divalent anion, for example, chloride, bromide, phosphate, orthosilicate, an organic acid, for example, a compound of the formula R 2b It can be an anion from a compound such as an organic acid having -COO- or an alkyl (having 1 to 40 carbon atoms) sulfonic acid. Here, R 2b is hydrogen, hydroxyl, or an alkyl group having from 1 to 40 carbon atoms.

[0026] From the viewpoint of fiber retention, examples of organic acids corresponding to the anion of A include acetic acid, propionic acid, phosphoric acid, glycolic acid, pyruvic acid, oxalic acid, maleic acid, malonic acid, succinic acid, fumaric acid, tartaric acid, citric acid, benzoic acid, cinnamic acid, mandelic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, glycyrrhizic acid, salicylic acid, stearic acid, phosphonic acid, trifluoroacetic acid, cyanoacetic acid, 4-cyanobenzoic acid, 2-chlorobenzoic acid, 2-nitrobenzoic acid, phenoxyacetic acid, and benzenesulfonic acid.

[0027] From the viewpoint of fiber retention, preferred bispyridinium compounds are compounds of general formula (2), and further octenidine dihydrochloride (R 1b is an n-octyl group, Y is an n-decenyl group, A is Cl, q is 1, and r is 2, CAS number 70775-75-6).

[0028] Examples of the nonionic surfactant of component (1-3) include, from the viewpoint of fiber retention, one or more selected from alkyl monoglyceryl ethers, polyoxyalkylene monoalkyl or alkenyl ethers, polyoxyalkylene fatty acid esters, sorbitan-based nonionic surfactants, aliphatic alkanolamides, fatty acid monoglycerides, and sucrose fatty acid esters.

[0029] From the viewpoint of fiber retention, the amphoteric surfactant of the component (1-4) may be one or more surfactants selected from betaine type surfactants and amine oxide type surfactants. Specifically, from the viewpoint of fiber retention, the component (1-4) may be one or more amphoteric surfactants selected from sulfobetaine, carbobetaine, and amine oxide.

[0030] From the viewpoint of fiber residual properties, examples of sulfobetaines include N-alkyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, in which the alkyl group preferably has 10 or more and 18 or less carbon atoms; N-alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, in which the alkyl group has 10 or more and 18 or less carbon atoms; N-alkanoylaminopropyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, in which the alkanoyl group has 10 or more and 18 or less carbon atoms; and N-alkanoylaminopropyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, in which the alkanoyl group has 10 or more and 18 carbon atoms.

[0031] From the viewpoint of fiber retention, examples of carbobetaines include N-alkyl-N,N-dimethyl-N-carboxymethylammonium betaines having an alkyl group with 10 to 18 carbon atoms and compounds represented by the following general formula.

[0032] [ka]

[0033] [In the formula, R 1c represents an alkyl or alkenyl group having 7 to 21 carbon atoms; R 2c represents a propylene group, and R 3c and R 4c each independently represents an alkyl group having 1 to 3 carbon atoms.

[0034] As the amine oxide, from the viewpoint of fiber retention, a compound of the following general formula is preferable.

[0035] [ka]

[0036] [In the formula, R 1d represents a hydrocarbon group having 7 to 22 carbon atoms, which is preferably an alkyl or alkenyl group from the viewpoint of fiber retention, more preferably an alkyl group; R 2d and R 3d are the same or different and each represents an alkyl group having 1 to 3 carbon atoms. D represents an -NHC(=O)- group or a -C(=O)NH- group, and E represents an alkylene group having 1 to 5 carbon atoms. m and p represent m=0 and p=0 or m=1 and p=1.

[0037] (2) pH adjuster From the viewpoint of fiber retention, an acidic or alkaline agent may be contained as a pH adjuster. The acid agent may be one or more selected from organic acids and inorganic acids. From the viewpoint of fiber retention, the organic acid may be one or more selected from citric acid, malic acid, acetic acid, succinic acid, tartaric acid, fumaric acid, lactic acid, propionic acid, oxalic acid, glutaric acid, adipic acid, gallic acid, mellitic acid, cinnamic acid, salicylic acid, phthalic acid, benzoic acid, pyruvic acid, oxaloacetic acid, and aconitic acid. From the viewpoint of fiber residue, the inorganic acid may be one or more selected from hydrochloric acid, phosphoric acid, sulfuric acid, boric acid, and carbonic acid. From the viewpoint of fiber retention, examples of the alkaline agent include inorganic alkaline agents such as alkali metal hydroxides and alkali metal carbonates, and alkanolamines in which one or more and three or less groups bonded to nitrogen atoms are alkanol groups having 2 to 4 carbon atoms, and the remaining are alkyl groups or hydrogen atoms having 1 to 4 carbon atoms. From the viewpoint of fiber retention, the alkanol group is preferably a hydroxyalkyl group, and more preferably a hydroxyethyl group. From the viewpoint of fiber retention, a hydrogen atom or a methyl group is preferable other than the alkanol group, and a hydrogen atom is particularly preferable. From the viewpoint of fiber retention, examples of the alkanolamine include alkanolamines such as 2-aminoethanol, N-methylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, and triethanolamine.

[0038] (3) Chelating agents From the viewpoint of fiber retention, specific examples of the chelating agent include aminopolyacetic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, and the like, or salts thereof; organic acids such as citric acid, lactic acid, tartaric acid, malic acid, and the like, or salts thereof; 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), and alkali metal or lower amine salts thereof.

[0039] (4) Anti-redeposition agents and / or polymeric dispersants From the viewpoint of fiber retention, examples of anti-redeposition agents and / or polymer-based dispersants include polyacrylic acid, polymaleic acid, carboxymethyl cellulose, and the like.

[0040] (5) Bleach From the viewpoint of fiber residual properties, examples of bleaching agents include hydrogen peroxide, sodium percarbonate, and sodium perborate.

[0041] (6) Bleach activator From the viewpoint of fiber residue, examples of bleach activators include tetraacetylethylenediamine and bleach activators represented by general formulas (I-2) to (I-7) of JP-A-6-316700.

[0042] (7) Enzymes From the viewpoint of fiber retention, the enzyme may be one or more enzymes selected from amylase, sucrase, maltase, lactase, pullulanase, fructofuranosidase, cellulase, protease and lipase.

[0043] (8) Fluorescent dyes From the viewpoint of fiber retention, examples of the fluorescent dye include fluorescent dyes commercially available as Tinopal CBS (trade name, manufactured by Ciba Specialty Chemicals) and Whitex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

[0044] (9) Antioxidants From the viewpoint of fiber retention, examples of the antioxidant include known antioxidant compounds such as butylated hydroxytoluene (common name: BHT), butylated hydroxyanisole (common name: BHA), distyrenated cresol, ascorbic acid (common name: vitamin C), tocopherol (common name: vitamin E), coffee bean extract (chlorogenic acid), and green tea extract (catechin), as well as known inorganic salts such as sodium sulfite and sodium hydrogen sulfite.

[0045] (10) From the viewpoint of fiber residue, colorants, fragrances, antibacterial preservatives other than component (a), ultraviolet protection agents, antifoaming agents such as silicones, etc.

[0046] (11) Organic solvents having a hydroxyl group From the viewpoint of fiber residue, one or more compounds selected from the following components (11-1) to (11-6) are used as the organic solvent having a hydroxyl group.

[0047] (11-1) Component: A monohydric alcohol having an aliphatic hydrocarbon group having 2 to 6 carbon atoms From the viewpoint of fiber retention, examples of the component (11-1) include monohydric alcohols selected from ethanol, 1-propanol, 2-propanol, and 1-butanol.

[0048] (11-2) Component: dihydric to hexahydric alcohol having 2 to 6 carbon atoms From the viewpoint of fiber retention, examples of the component (11-2) include dihydric or trihydric alcohols selected from ethylene glycol, propylene glycol, butylene glycol, 2-methyl-2,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, and glycerin. 2-Methyl-2,4-pentanediol is also called hexylene glycol.

[0049] Component (11-3): Polyalkylene glycol containing an alkylene glycol unit having 2 to 4 carbon atoms From the viewpoint of fiber retention, examples of the component (11-3) include polyalkylene glycols selected from diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols having a weight-average molecular weight of 400 or more and 4,000 or less, and polypropylene glycols having a weight-average molecular weight of 400 or more and 4,000 or less.

[0050] Component (11-4): a monoalkyl ether of (mono- or poly)alkylene glycol having an alkylene glycol unit having from 2 to 4 carbon atoms and an alkyl group having from 1 to 4 carbon atoms. From the viewpoint of fiber residue, examples of the component (11-4) include compounds selected from diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol.

[0051] (11-5) Component: Alkyl glyceryl ether having an alkyl group with 1 to 8 carbon atoms Examples of the (11-5) component, from the viewpoint of fiber retention, include alkyl glyceryl ethers selected from 1-methyl glyceryl ether, 2-methyl glyceryl ether, 1,3-dimethyl glyceryl ether, 1-ethyl glyceryl ether, 1,3-diethyl glyceryl ether, triethyl glyceryl ether, 1-pentyl glyceryl ether, 2-pentyl glyceryl ether, 1-octyl glyceryl ether, and 2-ethylhexyl glyceryl ether.

[0052] (11-6) Component: Aromatic alkyl ether of (mono- or poly-)alkylene glycol having an alkylene glycol unit having 2 or 3 carbon atoms From the viewpoint of fiber retention, examples of the (11-6) component include compounds selected from 2-phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, 2-benzyloxyethanol, and diethylene glycol monobenzyl ether.

[0053] In the above components (11-4) and (11-6), the term "(mono- or poly)alkylene glycol" means a monoalkylene glycol or a polyalkylene glycol. Also, the term "polyalkylene glycol" means a glycol containing 2 to 9 alkylene glycol units.

[0054] (12) Hydrotropes From the viewpoint of fiber retention, the hydrotrope is an organic compound having an anionic group, and further includes alkylbenzene carboxylic acid or alkylbenzene sulfonic acid having one or two alkyl groups selected from methyl, ethyl, or propyl groups and one sulfonic acid or carboxylic acid group, or a salt thereof, and benzoic acid or a salt thereof. More specifically, from the viewpoint of fiber retention, the hydrotrope is paratoluenesulfonic acid, cumenesulfonic acid, metaxylenesulfonic acid, or benzoic acid, and the salt is preferably an alkali metal salt.

[0055] (13)Fragrance From the viewpoint of fiber retention, the perfume has a masking effect and, in some cases, may itself be a substrate having deodorizing properties. As the fragrance, from the viewpoint of fiber retention, for example, the fragrances described in "Basic Knowledge of Fragrances and Fragrances, edited by Nakajima Mototaka, published by Sangyo Tosho Co., Ltd., 4th printing, April 20, 2005" and the fragrances described in JP-T-10-507793 can be used. In addition, the fragrance technology described in JP-A-2014-213072 can be used, and silicate ester fragrances and microcapsule fragrances can also be used.

[0056] (14) Deodorizing base material From the viewpoint of fiber residual property, examples of deodorizing base materials include polyhydroxyamine compounds described in JP 2018-29836 A. Examples of polyhydroxyamine compounds include tris(hydroxymethyl)aminomethane, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-hydroxyethyl-1,3-propanediol, and combinations of these with inorganic acids such as hydrochloric acid.

[0057] (15) Fabric softener From the viewpoint of fiber retention, the softener base is preferably a quaternary ammonium salt compound of the following general formula:

[0058] [ka]

[0059] [In the formula, R 1e , R 2e , R 3e are each independently a residue (acyl group) obtained by removing OH from a fatty acid having 16 to 22 carbon atoms, or a hydrogen atom. 1e , R 2e , R 3e At least one of R is an acyl group. 4e is an alkyl group having 1 to 3 carbon atoms; Z - is an anion.

[0060] The softening base may be a mixture of quaternary ammonium salt compounds of the general formula above. Such a mixture may be, for example, a mixture of quaternary ammonium salt compounds of the general formula above, 4e is an alkyl group having 1 to 3 carbon atoms; Z - A mixture of quaternary ammonium salts, where R is an organic or inorganic anion. 1e is a fatty acid residue (x) obtained by removing OH from a fatty acid having 16 to 22 carbon atoms, and R 2e and R 3e Compound (e1) in which R is a hydrogen atom; 1e and R 2e is the fatty acid residue (x), and R 3e Compound (e2) in which R is a hydrogen atom; 1e , R 2e and R 3e is the fatty acid residue (x).

[0061] R 1e , R 2e , R 3eFurthermore, from the viewpoint of fiber retention, the fatty acid residue (x) is preferably a residue obtained by removing OH (hydroxyl group) from a fatty acid having 16 or more and 22 or less carbon atoms, preferably 16 or more and 18 or less carbon atoms. Specific examples of fatty acids from the viewpoint of fiber retention include one or more selected from stearic acid, palmitic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, palm oil fatty acid, sunflower oil fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, safflower oil fatty acid, cottonseed oil fatty acid, corn oil fatty acid, olive oil fatty acid, hydrogenated palm oil fatty acid, beef tallow fatty acid, and hydrogenated beef tallow fatty acid. From the viewpoint of fiber retention, in the general formula, R 4e is preferably a methyl group or an ethyl group. From the viewpoint of fiber retention, in the general formula, Z - is an organic or inorganic anion, and is preferably an anion selected from a halogen ion such as a chlorine ion, an alkyl sulfate ion having 1 to 3 carbon atoms, a fatty acid ion having 12 to 18 carbon atoms, and a benzenesulfonate ion which may be substituted with 1 to 3 alkyl groups having 1 to 3 carbon atoms. From the viewpoint of fiber retention, in the present invention, an alkyl sulfate ion having 1 to 3 carbon atoms is more preferred, and a methyl sulfate ion or an ethyl sulfate ion is even more preferred. The quaternary ammonium salt compound of the general formula can be obtained by subjecting an esterification reaction product obtained by a method of subjecting a fatty acid to a dehydration esterification reaction with triethanolamine, or a method of subjecting a fatty acid lower alkyl ester (wherein the lower alkyl is a methyl group, an ethyl group, or a propyl group) to a transesterification reaction with triethanolamine, to a quaternization reaction with an alkylating agent.

[0062] (16) Fabric softener From the standpoint of fiber retention, examples of softening aids include polyhydric alcohol fatty acid esters such as glycerin, sorbitol, and pentaerythritol.

[0063] In the washing method of the present invention, the textile product to be rinsed contains component (a). The present invention has found that when rinsing a textile product containing component (a), if the rinsing liquid used for rinsing is water having a pH of 6.5 or less, the component (a) attached to the textile product is less likely to be washed away from the textile product, and the amount of component (a) remaining in the textile product can be increased. In the present invention, for example, after washing a textile product with a cleaning liquid containing component (a), the textile product containing component (a) can be rinsed. Usually, after washing, the textile product is dehydrated to separate the cleaning liquid, but after dehydration, the cleaning liquid containing component (a) is retained in the textile product before rinsing, and in the present invention, the textile product in such a state can be rinsed. Therefore, in the present invention, it is preferable to wash the textile product with a cleaning liquid containing component (a).

[0064] As the component (a), a phenol-based antibacterial compound is used from the viewpoint of fiber residue. The phenol-based antibacterial compound is an antibacterial compound having a phenol structure. Specific examples of component (a), from the viewpoint of residual properties on fibers, include phenol, cresol, thymol, carvacrol, eugenol, paraben, isopropylmethylphenol (common name: IPMP), chloroxylenol (common name: PCMX), o-benzyl-p-chlorophenol (common name: chlorophene), 4,4'-dichloro-2-hydroxydiphenyl ether (common name: diclosan), 5-chloro-2-(2,4-dichlorophenoxy)phenol (common name: triclosan), and benzylchlorophenol.

[0065] From the viewpoint of fiber residue, component (a) is preferably a compound having a halogen atom, more preferably a chlorodiphenyl ether antibacterial compound such as diclosan or triclosan, and even more preferably diclosan.

[0066] The component (a) may be used alone or in appropriate combination of two or more kinds.

[0067] In the present invention, rinsing is performed by contacting a water-containing rinse solution having a pH of 6.5 or less with a textile product containing the component (a). The raw material of the rinse solution may be ion-exchanged water or water containing hardness components such as tap water. When using water containing hardness components, the hardness of the water is, from the viewpoint of fiber residue, for example, 0.5° dH or more, more preferably 1° dH or more, even more preferably 2° dH or more, even more preferably 3° dH or more, and preferably 20° dH or less, more preferably 10° dH or less, even more preferably 8° dH or less, and even more preferably 6° dH or less. It is also preferable that the rinse solution has a hardness in this range. The German hardness is measured by the following method.

[0068] <Method of measuring water hardness in Germany> 〔reagent〕 0.01 mol / L EDTA·2Na solution: 0.01 mol / L aqueous solution of disodium ethylenediaminetetraacetate (titration solution, 0.01M EDTA-Na2, manufactured by Sigma-Aldrich) ·Universal BT indicator (product name: Universal BT, manufactured by Dojindo Laboratories Co., Ltd.) Ammonia buffer solution for hardness measurement (67.5 g of ammonium chloride dissolved in 570 ml of 28 w / v% ammonia water, and the total volume made up to 1000 ml with ion-exchanged water) [Method of measuring hardness] First, 20 mL of sample (raw water or rinse solution) is taken into a conical beaker with a whole pipette, and 2 mL of ammonia buffer solution for hardness measurement is added. Furthermore, 0.5 mL of Universal BT indicator is added, and it is confirmed that the solution after addition is reddish purple. While shaking the conical beaker well, add 0.01 mol / L EDTA·2Na solution from the burette and the end point of the titration is when the sample turns blue. The total hardness in the sample is calculated from the titration volume T (mL) of the EDTA·2Na solution using the following formula. Hardness (°DH)=(T×0.01×F×56.0774×100) / A T:0.01mol / L Titration amount of EDTA・2Na solution (mL) A: Sample volume (20 mL, sample volume) F: Factor of 0.01mol / L EDTA·2Na solution

[0069] In the present invention, the pH of the rinse solution is 6.5 or less, preferably 5.5 or less, more preferably 5.0 or less, and preferably 3.5 or more, more preferably 4.0 or more, from the viewpoint of fiber residue. From the viewpoint of fiber residue, the rinse solution only needs to have a pH of 6.5 or less when it comes into contact with the textile product, for example, at the start of rinsing, and the pH may vary during rinsing. Note that this pH is the pH at the temperature when rinsing is performed. The pH is measured by the following method.

[0070] [pH measurement method] A composite electrode for pH measurement (glass-ground sleeve type, manufactured by HORIBA) is connected to a pH meter (pH / ion meter F-23, manufactured by HORIBA) and the power is turned on. A saturated potassium chloride aqueous solution (3.33 mol / L) is used as the internal solution of the pH electrode. Next, a 100 mL beaker is filled with a pH 4.01 standard solution (phthalate standard solution), a pH 6.86 standard solution (neutral phosphate standard solution), and a pH 9.18 standard solution (borate standard solution), and the beaker is immersed in a thermostatic bath at 25°C for 30 minutes. The pH measurement electrode is immersed in the thermostatically adjusted standard solution for 3 minutes, and the calibration operation is performed in the order of pH 6.86 → pH 9.18 → pH 4.01. The sample to be measured (rinse solution) is adjusted to the temperature when rinsing is performed, and the electrode of the pH meter is immersed in the sample, and the pH is measured after 1 minute.

[0071] The pH of the rinse liquid may be adjusted by adding the aforementioned pH adjuster to the water.

[0072] In the present invention, from the viewpoint of increasing the amount of component (a) remaining in the textile product, the textile product contains component (a) in an amount of preferably 3 μg or more, more preferably 5 μg or more, and preferably 30 μg or less, more preferably 25 μg or less, even more preferably 20 μg or less, and still more preferably 15 μg or less, per gram of the textile product in a dry state before washing. Here, the amount of component (a) may be calculated as the amount of component (a) that comes into contact with 1 g of the textile product in a dry state before washing. For example, when a textile product is washed with a washing liquid containing component (a), the amount of component (a) may be calculated from the amount of the washing liquid used per 1 g of the textile product. In the present invention, the textile product can be washed with a washing liquid containing component (a) in an amount of 3 μg or more and 30 μg or less per gram of the textile product in a dry state before washing.

[0073] Examples of textile products include fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics using the hydrophobic and hydrophilic fibers, and products obtained using the fabrics, such as undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, knitted clothing, socks, underwear, tights, and masks. The fibers constituting the textile product may be either hydrophobic or hydrophilic. The fibers may be either natural fibers, chemical fibers, or a mixture of these. It is preferable that the textile product contains chemical fibers, since the residual effect of the component (a) according to the present invention is more easily manifested. Examples of hydrophobic fibers include protein fibers (milk protein casein fibers, Promix, etc.), polyamide fibers (nylon, etc.), polyester fibers (polyester, etc.), polyacrylonitrile fibers (acrylic, etc.), polyvinyl alcohol fibers (vinylon, etc.), polyvinyl chloride fibers (polyvinyl chloride, etc.), polyvinylidene chloride fibers (vinylidene, etc.), polyolefin fibers (polyethylene, polypropylene, etc.), polyurethane fibers (polyurethane, etc.), polyvinyl chloride / polyvinyl alcohol copolymer fibers (polycral, etc.), polyalkylene paraoxybenzoate fibers (benzoate, etc.), polyfluoroethylene fibers (polytetrafluoroethylene, etc.), glass fibers, carbon fibers, alumina fibers, silicone carbide fibers, rock fibers (rock fibers), slag fibers (slag fibers), and metal fibers (gold thread, silver thread, steel fiber). Examples of hydrophilic fibers include seed hair fibers (cotton, kapok, etc.), bast fibers (hemp, flax, ramie, hemp, jute, etc.), leaf vein fibers (Manila hemp, sisal, etc.), palm fibers, rush, straw, animal hair fibers (wool, mohair, cashmere, camel hair, alpaca, vicuna, angora, etc.), silk fibers (domestic silk, wild silk), feathers, and cellulosic fibers (rayon, polynosic, cupra, acetate, etc.).

[0074] From the viewpoint of fiber residual property, the temperature of the rinse liquid is preferably 0°C or higher, more preferably 3°C or higher, even more preferably 5°C or higher, and preferably 70°C or lower, more preferably 60°C or lower, even more preferably 50°C or lower, and still more preferably 40°C or lower.

[0075] From the viewpoint of fiber retention, the rinsing time is preferably 10 seconds or more, more preferably 30 seconds or more, and preferably 30 minutes or less, more preferably 20 minutes or less, even more preferably 15 minutes or less, and even more preferably 10 minutes or less.

[0076] Rinsing can be performed by rinsing with a pool of water, rinsing with running water, or a combination of these. The contact of the rinsing liquid with the textile product containing the component (a) can be carried out, for example, by supplying a previously prepared rinsing liquid having a pH of 6.5 or less to the textile product. Alternatively, the (a) component and a pH adjuster may be mixed into the cleaning agent, and the cleaning agent may be treated so that the (a) component and the pH adjuster remain in the washed textile product, and water (whose pH may be 6.5 or less or may be greater than 6.5) may be supplied to the washed textile product to adjust its pH to 6.5 or less, and the rinsing liquid having a pH of 6.5 or less may come into contact with the textile product, thereby performing the rinsing of the present invention. In general, when domestic water such as tap water is used for rinsing, the pH is close to neutral, so that if the textile product contains an acidic agent as a pH adjuster, the acidic agent functions as a pH lowering agent, and a rinsing liquid having a pH of 6.5 or less can be easily obtained. That is, if the cleaning liquid is acidic and water having a pH of more than 6.5 is supplied to a textile product containing the (a) component to adjust its pH to 6.5 or less, the rinsing of the present invention can be performed without the step of preparing rinsing water having a pH of 6.5 or less in advance.

[0077] The washing method of the present invention can be carried out, for example, in a washing machine for home or commercial use. In washing in a washing machine, a textile product is washed with a detergent, and then dehydrated as necessary, and then rinsed. In this case, the washing method of the present invention can be carried out by contacting a rinsing liquid having a pH of 6.5 or less with a textile product containing component (a) and rinsing it. Component (a) can be contained in the textile product to be rinsed by a method such as blending component (a) in a detergent or washing liquid, or supplying component (a) to the textile product before rinsing. In the present invention, the rinsing liquid may contain the cleaning agent and the components described in the cleaning liquid.

[0078] In the washing method of the present invention, from the viewpoint of fiber residue, a rotary washing machine can also be used for rinsing. From the viewpoint of fiber residue, specific examples of the rotary washing machine include a drum washing machine, a pulsator washing machine, and an agitator washing machine. These rotary washing machines can be commercially available for home use. In the present invention, it is preferable to use a drum washing machine, since the amount of water used for one wash can be further reduced.

[0079] The present invention provides a method for inhibiting the release of a phenolic antibacterial compound from a textile product, which comprises contacting a textile product having a phenolic antibacterial compound [component (a)] with a treatment solution containing water to treat the textile product, and setting the pH of the treatment solution to 6.5 or less. The items described in the washing method of the present invention can be appropriately applied to this method for inhibiting the release. This method for inhibiting the release can be incorporated into the washing method of the present invention, and can also be incorporated into, for example, a method for producing a textile product having antibacterial properties. EXAMPLES

[0080] (1) Preparation of rinsing solutions with different pH levels Wakayama City tap water (pH 7.5) was mixed with 0.1 M hydrochloric acid (Fujifilm Wako Pure Chemical Industries, Ltd.) to adjust the pH to 6.5, 6.0, 5.5, and 5.0 at 25°C to prepare rinse solutions. For pH measurements, a pH meter (HORIBA pH / ion meter D-71) was used that had been calibrated in advance with a pH 4.01 standard solution (phthalate standard solution), a pH 6.86 standard solution (neutral phosphate standard solution), and a pH 9.18 standard solution (borate standard solution).

[0081] (2) Preparation of test cloth 1.7 kg of cotton cloth (Cotton 2003 (Tanigashou Shoten)) was washed twice in a fully automatic washing machine (National NA-F702P) on the standard cycle (4.7 g of Emulgen 108 (Kao Corporation) during washing, 47 L of water, 9 minutes of washing, 2 rinses, 3 minutes of spin-drying), then washed three times in water only (47 L of water, 9 minutes of washing, 2 rinses, 3 minutes of spin-drying), and dried at 25°C for 24 hours. It was then cut into a size of 6 cm x 6 cm to prepare the cotton test cloth. A polyester fabric (polyester faille (manufactured by Tanigashira Shoten)) was treated in the same manner as above to prepare a synthetic fiber test fabric.

[0082] (3) Diclosan Residue Test An antibacterial agent (Tinosan HP100, BASF) containing diclosan, which is the component (a), was diluted with ethanol (FUJIFILM Wako Pure Chemical Industries, Ltd.) so that the diclosan concentration was 3, 15, and 30 μg / mL, and 0.4 mL was applied to one test cloth (0.4 g) and dried for 1 hour. Five test cloths (2 g) after drying and 40 g of rinse solution were placed in a screw tube No. 8 (Maruemu Co., Ltd.), and rinsed at 25 °C and 300 rpm for 10 minutes using a reciprocating shaker (TAITEC, STORONGSHAKER SA-2DW). The amount of diclosan applied to the test cloth corresponds to the amount of diclosan contained in the test cloth to be rinsed. After the rinsing process was completed, the test cloth was dehydrated using a 50 mL syringe (Terumo Co., Ltd.) and dried for 24 hours. Two randomly selected dried test cloths were sealed in screw tube No. 8 and the mass of the test cloth was measured. 50 mL of methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added thereto and ultrasonically treated for 30 minutes in an ultrasonic cleaner. The supernatant was then filtered through a PTFE filter (manufactured by Pall, pore size: 0.45 μm) to obtain a measurement solution. Next, Tinosan HP100 was diluted with methanol to prepare calibration curve solutions with diclosan concentrations of 0.015 μg / mL, 0.03 μg / mL, 0.15 μg / mL, 0.3 μg / mL, and 1.5 μg / mL. The amount of diclosan in the measurement solution was quantified using a liquid chromatography mass spectrometer (hereinafter abbreviated as LCMS device), and the amount of diclosan remaining on the test cloth from the calibration curve solution was determined. LCMS equipment: Shimadzu Corporation LCMS2020 Eluent A: 10mmol / L ammonium acetate in distilled water Eluent B: 10mmol / L ammonium acetate in methanol Gradient conditions: Eluent A / B = 1:1 (0 min) → Eluent B (2-5 min) → Eluent A / Eluent B = 1 / 1 (5.1 min-8 min), flow rate: 0.6 mL / min, sample injection volume 5 μL, column temperature 40°C The residual rate of diclosan on the test cloth was calculated using the following formula. The results are shown in Table 1. Dichrosan residual rate (%) = 100 x (amount of dichrosan remaining on the two test cloths (μg / 1g of test cloth)) / (amount of dichrosan applied to the two test cloths (μg / 1g of test cloth))

[0083] [Table 1]

[0084] From the results in Table 1, it can be seen that the residual rate of the component (a) is improved by rinsing the textile product with the component (a) (diclosan) attached thereto with a rinsing solution having a pH of 6.5 or less, as in the examples. In addition, in the examples, the residual rate of the component (a) is higher for synthetic fibers, and it can be seen that the method of the present invention is more effective for synthetic fibers. It is considered that even when the component (a) is mixed into a detergent and then rinsed, if the rinsing solution having a pH of 6.5 or less is brought into contact with the textile product with the component (a) attached thereto, the same tendency as in the examples in Table 1 will be observed. Therefore, even in the washing method in which the component (a) is mixed into a detergent, the effect of the present invention can be obtained by bringing the rinsing solution having a pH of 6.5 or less into contact with the textile product containing the component (a) and rinsing it. It is considered that the improvement in the residual rate of the component (a) leads to an improvement in the antibacterial effect.

Claims

1. A washing method for washing textile products and rinsing the washed textile products, comprising: The textile product to be rinsed contains (a) a phenolic antibacterial compound (hereinafter referred to as component (a)), Rinsing is carried out by contacting the textile product with a rinse solution containing water and having a pH of 6.5 or less. Washing instructions:

2. 2. The washing method according to claim 1, wherein the textile product contains 3 μg to 30 μg of component (a) per 1 g of the textile product in a dry state before washing.

3. 3. The washing method according to claim 1, wherein the textile product contains 5 μg or more and 25 μg or less of the component (a) per gram of the textile product in a dry state before washing.

4. 3. The washing method according to claim 1, wherein the pH of the rinse solution is 5.5 or less.

5. The washing method according to claim 1 or 2, wherein the component (a) is dichrosan.

6. The washing method according to claim 1 or 2, wherein the textile product contains chemical fibers.

7. 3. The washing method according to claim 1, wherein the textile product is washed with a washing liquid containing the component (a), and then the textile product containing the component (a) is rinsed.

8. A method for inhibiting the release of a phenolic antibacterial compound from a textile product, comprising contacting the textile product having the phenolic antibacterial compound adhered thereto with a treatment liquid containing water and adjusting the pH of the treatment liquid to 6.5 or less.