JP2024118357A - Method for manufacturing water-repellent textile structure and water-repellent chemical kit for textile structure - Google Patents

Abstract

To provide a method for producing a water-repellent fiber structure with high water repellency added with a fluorine-free water-repellent agent.SOLUTION: A method for producing a water-repellent fiber structure includes: an anionic polymer attachment step for attaching an anionic polymer (A) to a fiber structure; and a water-repellent treatment step for treating the fiber structure, to which the anionic polymer (A) has been attached, using a fluorine-free water-repellent (B) to render it water-repellent.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a water-repellent textile structure and a water-repellent treatment chemical kit for textile structures.

As a water repellent for use in textiles, etc., water repellent textile products using fluorine-based water repellents containing elemental fluorine are known (Patent Document 1, etc.).

JP 2004-262970 A

Fluorine compounds contained in fluorine-based water repellents, such as perfluorooctanoic acid (hereinafter referred to as "PFOA") and perfluorooctanesulfonic acid (hereinafter referred to as "PFOS"), may have an adverse effect on the living environment and living organisms. Therefore, in recent years, there has been a demand for textile products that use non-fluorine-based water repellents that do not contain fluorine element.

However, water-repellent textile products treated with non-fluorine-based water repellents have lower water repellency than textile products using fluorine-based water repellents, and in particular tend to lose water repellency after washing. For this reason, there is a need for a method for producing water-repellent textile products with high water repellency using non-fluorine-based water repellents.

Therefore, the present invention aims to provide a method for producing a water-repellent fiber structure with high water repellency using a non-fluorine-based water repellent agent, and a water-repellent chemical kit using a non-fluorine-based water repellent agent.

To achieve the above object, the method for producing a water-repellent textile structure of the present invention is characterized by including an anionic polymer attachment process step of attaching an anionic polymer (A) to a textile structure, and a water-repellent treatment process step of treating the textile structure to which the anionic polymer (A) has been attached with a non-fluorine-based water repellent agent (B) to make it water-repellent.

The water repellent treatment chemical kit for textile structures of the present invention is characterized by including an anionic polymer (A) and a non-fluorine-based water repellent agent (B).

The present invention provides a method for producing a water-repellent fiber structure with high water repellency using a non-fluorine-based water repellent agent, and a water-repellent chemical kit using a non-fluorine-based water repellent agent.

The present invention will be described below with reference to examples. However, the present invention is not limited to the following description.

In the present invention, a "fiber structure" refers to a structure made of fibers.

In the present invention, "textile product" refers to a product that uses a fiber structure.

In the present invention, the term "water repellent composition" refers to a water repellent that is a composition.

In the present invention, "isocyanate" refers to a compound having an isocyanate group (isocyanato group) -N=C=O in the molecule. "Monoisocyanate" refers to an isocyanate having only one isocyanate group in one molecule. "Polyisocyanate" refers to an isocyanate having multiple isocyanate groups in one molecule.

In the present invention, "alkyl" includes, for example, linear or branched alkyl. In the present invention, the alkyl group is not particularly limited, but examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icosyl group.

In the present invention, "alkylene" includes, for example, linear alkylene (methylene or polymethylene) or branched alkylene. In the present invention, the alkylene group is not particularly limited, but examples thereof include a methylene group, a dimethylene group (ethylene group), an ethylidene group, a trimethylene group, a 1-methylethylene group (propylene group), a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, a 1,1-dimethylethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decamethylene group.

The following describes the embodiments of the present invention in more detail. However, the present invention is not limited to the following embodiments.

[1. Method for producing water-repellent textile structure]
As described above, the method for producing a water-repellent fiber structure of the present invention is characterized by comprising an anionic polymer attachment treatment step of attaching an anionic polymer (A) to a fiber structure, and a water-repellent treatment step of treating the fiber structure to which the anionic polymer (A) has been attached with a non-fluorinated water repellent agent (B) to make it water-repellent.

[1-1. Anionic polymer (A)]
In the present invention, the term "anionic polymer" refers to a polymer capable of generating anions, for example, a polymer capable of generating a negative charge, i.e., an anion, when dissolved in water, and more specifically, for example, a polymeric substance having an anionic functional group.

In the present invention, the anionic polymer (A) is not particularly limited, but examples thereof include polyhydric phenol condensates, polyhydric phenol condensate derivatives, phenolsulfonic acid-formalin polycondensates, bisphenol S sulfone-formalin polycondensates, and thiophenol-formalin polycondensates. In the present invention, the "polyhydric phenol condensate" refers to, for example, a polymer or copolymer of a polyhydric phenol (an aromatic compound having multiple phenolic hydroxyl groups in one molecule). In the present invention, the "polyhydric phenol condensate derivative" refers to a compound in which the structure of a polyhydric phenol condensate has been changed, for example, a compound in which at least one hydrogen atom of a polyhydric phenol condensate has been substituted with a substituent. In the present invention, the anionic polymer (A) may be used alone or in combination of multiple types.

In the present invention, the anionic polymer (A) may be, for example, synthesized and used, or a commercially available product may be used. Examples of commercially available products include "Nylox 1500" manufactured by Lion Specialty Chemicals Co., Ltd., and further examples of the anionic polymers listed in Table 1 below.

In the present invention, the weight average molecular weight of the anionic polymer (A) is not particularly limited, but may be, for example, 1000 to 25000, or 2000 to 20000. In the manufacturing method of the water-repellent fiber structure of the present invention, the amount of the anionic polymer (A) added in the anionic polymer attachment treatment step is not particularly limited, but is preferably 0.2 to 20% o.w.f. of the fiber structure. In the present invention, "o.w.f." refers to the total mass (mass%) of the treatment agent (e.g., the anionic polymer (A) or the non-fluorinated water repellent agent (B)) when the total mass of the fiber structure to be treated is taken as 100 mass%.

In the present invention, the method for measuring the weight-average molecular weight of a substance (e.g., the anionic polymer (A), the non-fluorinated water repellent (B), etc.) is not particularly limited. For example, the weight-average molecular weight can be measured by GPC (gel permeation chromatography) under the following analysis conditions.

(Analysis conditions for anionic polymer (A))
Apparatus: Tosoh Corporation HLC-8320GPC
Detector: Differential refractive index detector (RI detector), polarity = (+)
Column: TSKgel guard column Super AW-H (4.6 mm I.D. x 3.5 cm), TSKgel Super AWM-H (6.0 mm I.D. x 15 cm) x 2, manufactured by Tosoh Corporation
Solvent: DMSO (Fujifilm Wako Pure Chemical Industries, Ltd., special grade), 60 mM LiBr (Fujifilm Wako Pure Chemical Industries, Ltd., special grade), 60 mM phosphoric acid (Fujifilm Wako Pure Chemical Industries, Ltd., special grade)
Flow rate: 0.4ml/min Temperature: 40℃

(Analysis conditions for non-fluorinated water repellent (B))
Apparatus: Waters e2695
Detector: Differential refractive index detector Waters 2414
Column: A total of three columns, HSPgel MB-H, RT2.0, and RT4.0 manufactured by Waters, were connected in series.
Solvent: Tetrahydrofuran Flow rate: 0.3 mL/min Temperature: 40° C.

[1-2. Non-fluorinated water repellent (B)]
In the present invention, the term "non-fluorine-based water repellent" refers to a water repellent that is substantially free of elemental fluorine. The term "substantially free of elemental fluorine" means that the mass of elemental fluorine contained in the non-fluorine-based water repellent (B) may be, for example, 1 mass% or less, 0.1 mass% or less, 0.01 mass% or less, 0.001 mass% or less, or 0.0001 mass% or less, with the total mass of the non-fluorine-based water repellent (B) being taken as 100 mass%, and the lower limit is not particularly limited, but may be, for example, 0 mass% or a numerical value exceeding 0 mass%. From the viewpoint of reducing the influence of fluorine on the living environment, living things, etc., it is preferable that the content of elemental fluorine contained in the non-fluorine-based water repellent (B) is as low as possible, and it is particularly preferable that the content of elemental fluorine contained in the non-fluorine-based water repellent (B) is 0 mass% (i.e., the non-fluorine-based water repellent (B) does not contain elemental fluorine at all).

In the present invention, the non-fluorinated water repellent (B) may contain, for example, an adduct (b) of the following components (b-1) and (b-2). The adduct (b) is a compound having a structure in which the following component (b-1) is added to an unsaturated bond of an isocyanate group (isocyanato group) in the following component (b-2). When the following component (b-1) is a vinyl-based polymer having a hydroxyl group, the adduct (b) is, for example, urethane. The "urethane" refers to a compound having a urethane bond (-NH-CO-O-). When the following component (b-2) is a vinyl-based polymer having at least one of an amino group and an imino group, the adduct (b) is, for example, urea. In the present invention, the "urea" refers to a urea derivative compound having a urea bond (-NH-CO-NH-), rather than urea itself.

(b-1) a vinyl polymer having at least one substituent selected from the group consisting of a hydroxyl group, an amino group, and an imino group; and (b-2) an isocyanate having an aliphatic group having 8 or more carbon atoms.

[1-2-1. Adduct (b)]
As described above, the component (b-1) is a vinyl polymer. The vinyl polymer is, for example, a polymer having a structure obtained by polymerizing a monomer having a terminal double bond (vinyl group CH ₂ ═CH— or vinylidene group CH ₂ ═C=). Examples of the monomer include vinyl alcohol, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, and vinyl benzoate. The vinyl polymer may have a structure of a copolymer of the monomer and another monomer. Examples of the other monomer include ethylene, propylene, 1-butene, isobutene, and 1-hexene. The vinyl polymer may be copolymerized with unsaturated carboxylic acids such as acrylamide, methacrylamide, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, as well as their esters, amides, and anhydrides; sulfonic acid monomers such as vinyl sulfonic acid; dimethylaminoethyl methacrylate, vinylimidazole, vinylpyridine, and vinylsuccinimide.

As described above, component (b-1) is a vinyl polymer having at least one substituent selected from the group consisting of hydroxyl groups, amino groups, and imino groups, and may be, for example, a vinyl polymer having a hydroxyl group. Examples of the vinyl polymer having a hydroxyl group include polyvinyl alcohol, vinyl alcohol-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and ethylene-vinyl alcohol-vinyl acetate copolymer. When component (b-1) is an ethylene-vinyl alcohol copolymer, the content of the vinyl alcohol structural unit is not particularly limited, but is, for example, 10 to 80 mol%, 40 to 80 mol%, or 40 to 70 mol%. The average degree of polymerization of the ethylene-vinyl alcohol copolymer is not particularly limited, but is, for example, 100 or more, 500 or more, or 800 or more, and is, for example, 3,000 or less, 2,500 or less, or 1,500 or less. Examples of commercially available ethylene-vinyl alcohol copolymers include EVAL (Grades E-171B, E-151B, E-105B, E-171A, E-151A, and E-105A) manufactured by Kuraray Co., Ltd., and Soarnol (Grades AT4403, AT4406, and A4412) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Also usable are ethylene-vinyl alcohol copolymers to which ethylene oxide has been added, which are synthesized by addition polymerization of ethylene oxide to the vinyl groups of ethylene-vinyl alcohol copolymers. Examples of commercially available products include Sumiguard Grade 300K and Sumiguard Grade 300G manufactured by Sumitomo Chemical Co., Ltd. When component (b-1) is polyvinyl alcohol, the average degree of polymerization is not particularly limited, but is, for example, 100 to 3,000 or 150 to 2,000. The degree of saponification of the polyvinyl alcohol is also not particularly limited, but is, for example, 70% or more, 80% or more, or 90 to 100%.

Component (b-1) may be, for example, a vinyl polymer having an amino group, or a vinyl polymer having an imino group. Component (b-1) may be, for example, a vinyl polymer having only either an amino group or an imino group, or a vinyl polymer having both. Examples of the vinyl polymer having at least one of an amino group and an imino group include polyallylamine and polyethyleneimine. The molecular weight of the polyallylamine and polyethyleneimine is not particularly limited, but is, for example, 300 to 100,000.

Only one type of component (b-1) may be used, or two or more types may be used in combination. For example, as described above, component (b-1) may be at least one selected from the group consisting of polyvinyl alcohol, vinyl alcohol-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl alcohol-vinyl acetate copolymer, polyallylamine, and polyethyleneimine.

As described above, component (b-2) is an isocyanate having an aliphatic group having 8 or more carbon atoms. Component (b-2) may be a monoisocyanate or a polyisocyanate, but is, for example, a monoisocyanate. Examples of the aliphatic group include an alkyl group, an alkenyl group, an alkynyl group, and the like, and is preferably an alkyl group. The aliphatic group may be branched, but is preferably linear. The number of carbon atoms in the aliphatic group is 8 or more, and the upper limit is not particularly limited, but is, for example, 30 or less, or 20 or less. Examples of component (b-2) include monoalkyl isocyanates such as octyl isocyanate, dodecyl isocyanate (lauryl isocyanate), and octadecyl isocyanate (stearyl isocyanate), and particularly preferably octadecyl isocyanate (stearyl isocyanate). In addition, as for the octadecyl isocyanate, a mixture containing monoalkyl isocyanates having, for example, 12, 14, 16, 17, 18, or 20 carbon atoms in the alkyl group is commercially available, and such a mixture may be used. The content ratio of each component in the mixture is preferably 1 to 10 mass% of isocyanate having an alkyl group with 16 carbon atoms, 0.5 to 4 mass% of isocyanate having an alkyl group with 17 carbon atoms, and 80 to 98 mass% of alkyl group having 18 carbon atoms. In addition, the mixture is, for example, a mixture in which the mixing ratio of the main components is 8 to 9 mass% of isocyanate having an alkyl group with 16 carbon atoms, 3 to 4 mass% of isocyanate having an alkyl group with 17 carbon atoms, and 85 to 87 mass% of isocyanate having 18 carbon atoms. An example of a commercially available product of such a mixture is, for example, Millionate O, a product of Hodogaya Chemical Co., Ltd. In the present invention, component (b-2) may be used alone or in combination of two or more types.

In the adduct (b), the ratio of the total number of hydroxyl groups, amino groups, and imino groups in component (b-1) to the number of isocyanate groups in component (b-2) is not particularly limited, but may be, for example, 4/1 to 1/1 as described above, or may be, for example, 4/3 to 1/1 or 2/1 to 1/1.

The method for producing the adduct (b) is not particularly limited, and may be the same as or equivalent to the addition reaction between a general hydroxyl group-containing polymer or imino group-containing polymer and an isocyanate. Specifically, the method for producing the adduct (b) can be carried out, for example, as follows.

First, component (b-1) (polymer) may or may not be dehydrated as necessary. The dehydration is not particularly limited, but for example, the particulate component (b-1) is dispersed in a non-polar solvent such as toluene and azeotropically dehydrated. Other methods include, for example, a method of removing water using a dryer or the like. From an industrial standpoint of efficiency, azeotropic dehydration is preferred. As an azeotropic dehydration operation, for example, a method of separating and removing water midway through the reflux device while refluxing may be used. In addition, the solvent used is not particularly limited as long as it is a solvent that forms an azeotrope with water, but toluene and xylene are preferred in terms of solubility with the water repellent of the present invention. The water content in component (b-1) after the water removal process is not particularly limited, but it is preferable to make it 150 ppm or less.

Next, the component (b-1) is reacted with a catalyst used in a general urethanization reaction with an isocyanate, if necessary. For example, one or more of the following reaction catalysts may be added: tertiary amines and their salts, highly water-soluble weakly acidic alkali metal salts, organic zirconium compounds, organic titanium compounds, zinc salts, zirconium complexes, bismuth salts, aluminum compounds, inorganic tin compounds, inorganic bismuth compounds, etc. From the viewpoint of reducing the environmental load, it is preferable to avoid using organometallic compounds such as dibutyltin dilaurate. When using a catalyst, a water-soluble solvent such as dimethyl sulfoxide or a water-insoluble solvent such as toluene may be added as necessary. The catalyst may be, for example, a commercially available catalyst. The commercially available catalyst may be, for example, the catalysts listed in Table 2 below, and one type may be used alone or two or more types may be used in combination.

Next, component (b-2) (isocyanate) is added and reacted. As described above, the catalyst is added before the reaction, but it may be added during the reaction or in multiple batches. The reaction temperature and reaction time are not particularly limited, and may be the same as or equivalent to the addition reaction of a general hydroxyl group-containing polymer or imino group-containing polymer with an isocyanate. The reaction temperature is not particularly limited as described above, but may be, for example, 50 to 150°C or 75 to 140°C. The reaction time may be, for example, 100 to 240 minutes or 120 to 200 minutes. The end point of the reaction can be confirmed, for example, by measuring the amount of unreacted isocyanate compound remaining in the reaction mixture using an infrared spectrophotometer.

After the reaction is completed, for example, water can be added to separate the oil layer and the water layer, and the catalyst can be removed by transferring it to the water layer. Note that, for example, if the removal of the catalyst is not necessary, this operation may be omitted. On the other hand, the adduct (b) of the target product transfers to the oil layer. This oil layer may be filtered through a filter to remove by-products (e.g., bis-urea bodies). Note that, for example, if the removal of the by-products is not necessary, this operation may be omitted. The filter is not particularly limited, but since the purpose is to remove by-products that are insoluble in organic solvents such as toluene, a closed pressure filter is preferable. The filtration method is not particularly limited, and for example, either a method in which the solution is passed from a vessel containing the solution through a filter and received in another vessel, or a circulation method in which the solution is passed from a vessel containing the solution through a filter and returned to the vessel containing the solution again, can be used.

The oil layer containing the adduct (b) is then placed in a vessel that has already been charged with methanol, and the precipitated adduct (b) is separated by filtration and used in the water repellent of the present invention. For example, when the separation step of the catalyst and the by-products is omitted, the mixture after completion of the reaction may be directly placed in methanol to precipitate the adduct (b).

[1-2-2. Manufacturing method of non-fluorinated water repellent agent (B)]
In the present invention, the non-fluorinated water repellent (B) may consist of only the adduct (b), but may further contain other components other than the adduct (b). The non-fluorinated water repellent (B) may further contain, for example, a surfactant (b-3) and water (C) in addition to the adduct (b). The non-fluorinated water repellent (B) may further contain, for example, an organic solvent (D) in addition to the adduct (b), and the adduct (b) may be dissolved in the organic solvent (D). Hereinafter, the former may be referred to as a "water-based water repellent" and the latter as a "solvent-based water repellent".

The method for producing the water-based water repellent is not particularly limited, but for example, a general mechanical emulsification method can be used. The machine used in the mechanical emulsification method is not particularly limited, but for the batch method, examples include a Nauta mixer, an anchor mixer, a homomixer, a homodisper, a planetary mixer, etc., and a multi-axis emulsification and dispersion device that combines these, such as the Combimix series manufactured by Primix Corporation, can be used. For the continuous method, examples include a line homomixer, etc., or a device that combines these can be used. In particular, a high-temperature, high-pressure emulsification and dispersion device that can create high pressure inside the device is preferable.

In the water-based water repellent, the surfactant (b-3) is not particularly limited, and may be, for example, a general surfactant. The surfactant may be, for example, a nonionic surfactant, a cationic surfactant, an anionic surfactant, or an amphoteric surfactant. Examples of nonionic surfactants include polyoxyalkylene alkyl ether surfactants such as polyoxyethylene alkyl ether surfactants, polyoxyalkylene alkylamines, etc. Examples of polyoxyalkylene alkyl ether surfactants include products under the trade names Brownon 230 and Fine Surf 1502.2 manufactured by Aoki Oil & Fat Co., Ltd. Examples of cationic surfactants include, for example, quaternary ammonium salts, tertiary amines or salts thereof, etc. Examples of the quaternary ammonium salts include, for example, Lipocard 18-63 manufactured by Lion Specialty Chemicals Co., Ltd. Examples of anionic surfactants include, for example, alkylbenzene sulfonic acid and its salts, fatty acid salts, etc. Examples of amphoteric surfactants include, for example, fatty acid amidopropyl dimethylaminoacetic acid betaine, etc. The surfactant (b-3) may be used alone or in combination with two or more types.

In the water-based water repellent, the content of the surfactant (b-3) is not particularly limited, but is, for example, 1% by mass or more, 3% by mass or more, or 5% by mass or more relative to the mass of the adduct (b), and is, for example, 200% by mass or less, 150% by mass or less, or 100% by mass or less.

The water-based water repellent may further contain organic compounds such as hydrocarbon oils and higher alcohols. The organic compounds such as hydrocarbon oils and higher alcohols are components different from the organic solvent mixed with water (C) in the water-based water repellent described below. Specific examples of the hydrocarbon oil include squalene, squalane, liquid paraffin, liquid isoparaffin, heavy liquid isoparaffin, α-olefin oligomer, cycloparaffin, polybutene, petrolatum, paraffin wax, microcrystalline wax, polyethylene wax, and ceresin. The higher alcohol is a higher alcohol having 6 to 30 carbon atoms, and specific examples include hexyl alcohol, 2-ethylhexyl alcohol, octyl alcohol, decyl alcohol, isodecyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, icosyl alcohol, and behenyl alcohol. The content of the organic compound is not particularly limited, but is, for example, 1% by mass or more, 3% by mass or more, or 5% by mass or more, and, for example, 200% by mass or less, 150% by mass or less, or 100% by mass or less, relative to the mass of the adduct (b). The organic compound has, for example, an effect of reducing the viscosity of the water-based water repellent. For example, during the production of the water-based water repellent of the present invention, by adding an organic compound that has an effect of reducing the viscosity of the water-based water repellent, the behavior of the viscosity increasing can be controlled, and emulsification dispersion can be easily performed.

In the water-based water repellent, the water (C) is not particularly limited, and examples thereof include tap water, distilled water, and ion-exchanged water. If necessary, the water (C) may be mixed with an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent that is miscible with water, and examples thereof include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol, and glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether. The ratio of water to the organic solvent is not particularly limited.

In addition, in the water-based water repellent, the content of the additive (b) is not particularly limited, but is, for example, 0.5% by mass or more, 1% by mass or more, or 3% by mass or more relative to the mass of water (C), and is, for example, 90% by mass or less, 70% by mass or less, or 50% by mass or less.

In the solvent-based water repellent, the organic solvent (D) is not particularly limited, but is preferably a solvent that easily dissolves the adduct (b). Examples of the organic solvent (D) include hydrocarbon solvents such as aromatic hydrocarbons and aliphatic hydrocarbons (normal hexane, etc.), alcohol solvents (methanol, ethanol, etc.), glycol solvents (ethylene glycol, etc.), amide solvents (dimethylformamide (DMF), dimethylacetamide, etc.), sulfoxide solvents (dimethyl sulfoxide, etc.), ketone solvents (methyl ethyl ketone (MEK)), aromatic solvents (toluene, xylene, etc.), ether solvents (dioxane, tetrahydrofuran, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), etc. Examples of the aromatic hydrocarbons include toluene, benzene, xylene, and 1,3,5-trimethylbenzene. The organic solvent (D) may be used alone or in combination of two or more types.

In addition, in the solvent-based water repellent, the content of the additive (b) is not particularly limited, but is, for example, 0.1 mass% or more, 0.5 mass% or more, or 1.0 mass% or more relative to the mass of the organic solvent (D), and is, for example, 90 mass% or less, 80 mass% or less, or 70 mass% or less.

As described above, the non-fluorine-based water repellent (B) may or may not contain optional components other than the component (b-1). In addition to the above-mentioned components, the optional components include, for example, amino-modified silicone (E). That is, the water-based water repellent or solvent-based water repellent that is the non-fluorine-based water repellent (B) may further include amino-modified silicone (E). By including amino-modified silicone (E), for example, the water repellency of the water-repellent treated fiber or fiber product is further improved, or the texture becomes softer. Examples of amino-modified silicone (E) include side-chain type amino-modified silicone, both-end type amino-modified silicone, one-end type amino-modified silicone, and side-chain both-end type amino-modified silicone, and may have different reactive groups such as polyether groups in the same molecule. Examples of the amino-modified silicone include SM-8709SR, a product name manufactured by Toray Dow Corning Co., Ltd. In the amino-modified silicone, the functional group equivalent of the amino group is not particularly limited, but is, for example, 100 to 20,000 g/mol, 200 to 18,000 g/mol, or 500 to 16,000 g/mol.

In the aqueous water repellent or solvent-based water repellent, the content of the amino-modified silicone (E) is not particularly limited, but is, for example, 0.5% by mass or more, 1% by mass or more, or 2% by mass or more relative to the mass of the adduct (b), and is, for example, 200% by mass or less, 150% by mass or less, or 100% by mass or less.

In the aqueous water repellent or solvent-based water repellent, the optional components other than the amino-modified silicone (E) include, for example, straight silicone oils such as dimethyl silicone oil and methyl hydrogen silicone oil, and reactive silicone oils such as polyether-modified silicone oil and epoxy-modified silicone oil.

The method for producing the water-based water repellent or the solvent-based water repellent is not particularly limited, and may be, for example, simply mixing all the components and dissolving or dispersing them. In addition, each component may be dissolved or dispersed while being heated or the like as appropriate so as to make it easier to dissolve or disperse. For example, in the case of a water-based water repellent, the adduct (b) and the surfactant (b-3) may be mixed while being heated and stirred, and then water (C) may be added while continuing to be heated and stirred to disperse the adduct (b) and the surfactant (b-3) in the water (C), thereby producing the water-based water repellent. The heating temperature in this case is not particularly limited, and may be, for example, 30°C or higher, or 50°C or higher, and, for example, 180°C or lower, or 160°C or lower. The heating and stirring time is not particularly limited, and may be, for example, until all the components are uniformly mixed.

[1-3. Anionic polymer attachment treatment process]
As described above, the method for producing a water-repellent fiber structure of the present invention is characterized by including an anionic polymer attachment treatment step of attaching an anionic polymer (A) to a fiber structure, and a water-repellent treatment step of treating the fiber structure to which the anionic polymer (A) has been attached with a non-fluorinated water repellent agent (B) to make it water-repellent. Other than this, the method for producing a water-repellent fiber structure of the present invention is not particularly limited, and may or may not include any step other than the anionic polymer attachment treatment step and the water-repellent treatment step. Specifically, the method for producing a water-repellent fiber structure of the present invention can be performed, for example, as follows.

First, the anionic polymer attachment process is performed to attach an anionic polymer (A) to a fiber structure. The fiber structure to which the anionic polymer (A) is attached is not particularly limited, but examples include 100% nylon fabric, 100% polyester fabric, blends, woven fabrics, knits, and yarns. According to the present invention, for example, a non-fluorine-based water repellent can be used to impart water repellency or water/oil repellency with high washing durability to polyester-based fiber structures and nylon-based fiber structures that do not have ionic polarity or have low ionic polarity. In the present invention, the term "polyester-based fiber structure" refers to a fiber structure containing polyester, and the term "nylon-based fiber structure" refers to a fiber structure containing nylon.

As mentioned above, the fiber structure is not particularly limited, but may be, for example, a dyed fiber structure.

According to the anionic polymer attachment process, for example, the anionic polymer (A) can be imparted to a fiber structure that does not have ionic polarity or has a small ionic polarity as described above, by affinity to the fiber due to van der Waals forces, hydrogen bonds, intermolecular bonds, etc. By the anionic polymer attachment process, for example, when a water repellent treatment is performed with the non-fluorine-based water repellent (B), which is a post-processing agent, the non-fluorine-based water repellent (B) can be firmly adsorbed to the fiber structure, improving the coating strength. According to the manufacturing method of the water-repellent fiber structure of the present invention, for example, a water-repellent fiber product with excellent washing durability can be provided.

Next, the anionic polymer (A) is attached to the fiber structure. This method is not particularly limited, but for example, the fiber structure may be immersed in an aqueous solution of the anionic polymer (A). The method for this is also not particularly limited, but for example, any method may be used, such as a batch method, a continuous method, or a spray method. From the viewpoint of more reliably attaching (adsorbing) the anionic polymer (A) to the fiber structure, the batch method is particularly preferred, and the exhaust method is also preferred.

The bath ratio in the batch method, i.e., the weight ratio of the treatment bath to the fiber structure (cellulosic fiber: treatment bath), is not particularly limited, but can be, for example, in the range of 1:10 to 1:50. The treatment temperature is also not particularly limited, but can be, for example, 50 to 100°C. The amount of the anionic polymer compound (A) used is also not particularly limited, but for example, 0.2 to 20% owf. relative to the weight of the fiber structure, as described above. The concentration of the treatment liquid (aqueous solution of the anionic polymer (A)) used is also not particularly limited and can be set appropriately, but may be, for example, 0.5 to 15% by mass, 1 to 10% by mass. The pick-up rate is also not particularly limited, but may be, for example, 30 to 100% by mass, 40 to 80% by mass. The pick-up rate refers to the weight ratio of the treatment liquid attached to the fiber structure before immersion after the fiber structure is immersed in the treatment liquid. The immersion time in the treatment liquid is not particularly limited and can be set appropriately, but may be, for example, 10 seconds or more, 30 seconds or more, 1 minute or more, 2 minutes or more, or 5 minutes or more, or may be, for example, 120 minutes or less, 100 minutes or less, 80 minutes or less, 60 minutes or less, or 40 minutes or less.

In the continuous method, the fiber structure can be treated by immersing it in an aqueous solution of the anionic polymer (A) as described above. The concentration of the treatment liquid (aqueous solution of the anionic polymer (A)) used is not particularly limited and can be set appropriately, and may be, for example, 0.5 to 15 mass %, 1 to 10 mass %. The pick-up rate is also not particularly limited and may be, for example, 30 to 100 mass %, 40 to 80 mass %. The pick-up rate refers to the weight ratio of the treatment liquid attached to the fiber structure before immersion after immersing the fiber structure in the treatment liquid. The immersion time in the treatment liquid is also not particularly limited and can be set appropriately, and may be, for example, 0.1 seconds or more, 1 second or more, 5 seconds or more, 10 seconds or more, or 30 seconds or more, and may be, for example, 5 minutes or less, 3 minutes or less, or 1 minute or less.

In this manner, the anionic polymer attachment process step of attaching the anionic polymer (A) to the fiber structure can be performed. After the anionic polymer attachment process step, for example, the excessively attached anionic polymer compound (A) may be removed. The removal method is not particularly limited, and for example, the fiber structure to which the anionic polymer compound (A) is attached may be washed with hot water or water. In addition, for example, after the anionic polymer attachment process step, the fiber structure may be dried. The drying method, drying temperature, and drying time are not particularly limited and can be set appropriately, and for example, the fiber structure may be dried by air drying, or dried at 50 to 100°C for 30 seconds to 1 minute.

Next, the water-repellent treatment step is performed in which the fiber structure to which the anionic polymer (A) is attached is treated with a non-fluorine-based water-repellent agent (B) to make it water-repellent. The method for performing the water-repellent treatment step is not particularly limited except for performing the water-repellent treatment with the non-fluorine-based water-repellent agent (B), and may be, for example, the same as or similar to the water-repellent treatment method for general fibers or fiber products.

Specifically, the water repellent treatment process can be carried out, for example, as follows:

First, a treatment liquid containing the non-fluorine-based water repellent (B) is prepared. For example, the non-fluorine-based water repellent (B) may be used as the treatment liquid as it is, or may be diluted with water or an organic solvent to form the treatment liquid. For example, in the case of a water-based water repellent, it may be diluted with water to form the treatment liquid, and in the case of a solvent-based water repellent, it may be diluted with an organic solvent of the same type or a different type as the organic solvent (D) to form the treatment liquid. The concentration of the treatment liquid is not particularly limited, but the concentration of the adduct (b) of the components (b-1) and (b-2) is, for example, 0.1 mass% or more, 0.3 mass% or more, or 0.5 mass% or more relative to the dispersion medium or solvent of the treatment liquid (for example, the water or organic solvent), and is, for example, 30 mass% or less, 20 mass% or less, or 10 mass% or less.

The treatment liquid may or may not contain any additive other than the non-fluorine-based water repellent (B). The additives are not particularly limited, but examples include water repellents other than the non-fluorine-based water repellent (B), resins, surfactants, penetrating agents, defoamers, pH adjusters, antibacterial agents, colorants, antioxidants, chelating agents, deodorants, antistatic agents, catalysts, crosslinking agents, antibacterial and deodorant agents, flame retardants, softeners, and wrinkle inhibitors.

In addition, for example, a water-repellent aid may be added to the treatment liquid. The water-repellent aid is not particularly limited, but examples thereof include straight silicone oils such as amino-modified silicone oil, dimethyl silicone oil, and methyl hydrogen silicone oil, and reactive silicone oils such as polyether-modified silicone oil and epoxy-modified silicone oil. The amount of the water-repellent aid added is also not particularly limited, but is, for example, 0.5% by mass or more, 1% by mass or more, or 2% by mass or more relative to the adduct (b), and is, for example, 200% by mass or less, 150% by mass or less, or 100% by mass or less.

Next, the water-repellent treatment step is performed to treat the fibers with the treatment liquid to make them water-repellent. This water-repellent treatment step may be similar to or equivalent to the water-repellent treatment method for general fibers or textile products, as described above. Specifically, for example, the treatment liquid may be impregnated into the fibers or textile products to be treated for water repellency, and then the fibers or textile products may be dried. In this manner, the method for manufacturing the water-repellent textile product of the present invention can be performed. Note that the method for manufacturing the water-repellent textile product of the present invention may or may not include other steps in addition to the water-repellent treatment step. Examples of the other steps include the dry heat treatment described below.

The water repellent treatment process may be carried out, for example, by a continuous method or a batch method.

In the continuous method, for example, first, the fiber or textile product to be treated is continuously fed into an impregnation device filled with the treatment liquid, and the water-repellent treatment liquid is impregnated into the treated material, after which unnecessary water-repellent treatment liquid is removed. The impregnation device is not particularly limited, but a padder type applicator, a kiss roll type applicator, a gravure coater type applicator, a spray type applicator, a foam type applicator, or a coating type applicator is preferred, with a padder type being particularly preferred. Next, water, organic solvents, etc. remaining on the treated material are removed using a dryer. The dryer is not particularly limited, but a hot flue, tenter, or other spreader dryer is preferred. The continuous method is preferably used, for example, when the treated material is a fabric such as a woven fabric.

The batch method includes, for example, an immersion step in which the fiber or textile product to be treated is immersed in the treatment liquid, and a liquid removal step in which water, organic solvents, etc. remaining in the treated object immersed in the water-repellent treatment liquid are removed. The batch method is preferably used, for example, when the treated object is not suitable for treatment by a continuous method. More specifically, examples of the treated object include a case in which the treated object is not in the form of a fabric, such as a case in which the treated object is loose hair, top, sliver, skein, tow, yarn, etc., or a case in which the treated object is a knitted fabric. In the immersion step, for example, a cotton dyeing machine, a cheese dyeing machine, a liquid flow dyeing machine, an industrial washing machine, a beam dyeing machine, etc. can be used. In the liquid removal step, for example, a cheese dryer, a beam dryer, a hot air dryer such as a tumble dryer, a high-frequency dryer, etc. can be used.

In addition, for example, in the water-repellent treatment step, the treatment liquid may contain isocyanate (F) and the adduct (b) may be crosslinked by the isocyanate (F). For example, when the treatment liquid contains amino-modified silicone (E), the amino group of the amino-modified silicone (E) may be crosslinked with the isocyanate (F). By adding isocyanate (F), for example, the water repellency (washing durability) of the water-repellent textile product after washing is further improved. The isocyanate (F) is not particularly limited, but for example, an organic compound containing two or more isocyanate functional groups in the molecule can be used. Specific examples of the isocyanate (F) include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, triphenyl triisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, trimethylolpropane tritolylene diisocyanate adduct, glycerin tritolylene diisocyanate adduct, uret of hexamethylene diisocyanate, trimethylolpropane trihexamethylene diisocyanate adduct, and glycerin trihexamethylene diisocyanate adduct. Further, the isocyanate (F) may be an organic compound containing a blocked isocyanate functional group, which is obtained by reacting the organic compound containing the isocyanate functional group with phenol, diethyl malonate, methyl ethyl ketoxime, sodium bisulfite, ε-caprolactam, or the like, which dissociates when heated to regenerate an active isocyanate group, to block the isocyanate group. Specific examples of the isocyanate (F) include solvent-based products such as Coronate B-45E and Coronate HX manufactured by Tosoh Corporation, and Duranate D101 and Duranate D201 manufactured by Asahi Kasei Corporation, and water-based products such as the "Aquanate" series manufactured by Tosoh Corporation, Duranate WB40-100, Duranate WT20-100, and Duranate WE50-100 manufactured by Asahi Kasei Corporation, and the "Elastron" series manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

As the isocyanate (F), for example, Elastron BN-11 (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. may be used as in the examples described later, and other examples include the isocyanate crosslinking agents listed in Table 3 below.

The amount of isocyanate (F) added is not particularly limited, and is, for example, 0.5% by mass or more, 1% by mass or more, or 3% by mass or more, and, for example, 200% by mass or less, 150% by mass or less, or 100% by mass or less, relative to the adduct (b). In the crosslinking reaction in which the adduct (A) is crosslinked with the isocyanate (F), the reaction temperature is not particularly limited, and is, for example, 100°C or more, or 120°C or more, and, for example, 200°C or less, or 180°C or less. The reaction time is not particularly limited, and is, for example, 0.1 minutes or more, or 0.3 minutes or more, and, for example, 20 minutes or less, or 15 minutes or less.

In this manner, the water-repellent treatment process is carried out to make the fiber structure to which the anionic polymer (A) is attached water-repellent with a non-fluorine-based water repellent agent (B), thereby producing a water-repellent fiber structure.

It is preferable to perform a dry heat treatment on the water-repellent fiber structure that has been treated with a non-fluorine-based water repellent (B). This is because the dry heat treatment makes it easier for the active ingredient of the non-fluorine-based water repellent (B) to adhere more firmly to the water-repellent fiber structure. However, the present invention does not require a dry heat treatment. The method for producing a water-repellent fiber structure of the present invention can also be used for fiber structures such as paper products and wood boards (e.g., particle boards, MDF boards, etc.).

[2. Water-repellent chemical kits, water-repellent textile products, etc.]
As described above, the water-repellent chemical kit of the present invention contains an anionic polymer (A) and a non-fluorinated water repellent (B). The water-repellent chemical kit of the present invention may or may not contain optional components other than the anionic polymer (A) and the non-fluorinated water repellent (B). The optional components may be, for example, each component described in the method for producing a water-repellent fiber structure of the present invention.

The water-repellent chemical kit of the present invention can be used, for example, in the method for producing the water-repellent fiber structure of the present invention.

According to the water-repellent chemical kit of the present invention or the method for producing a water-repellent fiber structure of the present invention, for example, as described above, a water-repellent fiber product having excellent water repellency can be produced. In addition, according to the water-repellent chemical kit of the present invention or the method for producing a water-repellent fiber structure of the present invention, for example, a water-repellent product having excellent water repellency after washing (washing durability) can also be produced. According to the water-repellent chemical kit of the present invention or the method for producing a water-repellent fiber structure of the present invention, it is possible to exhibit water repellency or washing durability equivalent to that of a fluorine-based water repellent, for example.

In addition, according to the water-repellent chemical kit of the present invention or the method for producing a water-repellent fiber structure of the present invention, for example, excellent oil repellency can be obtained. This allows, for example, a water-repellent fiber product with excellent oil repellency to be produced. In addition, for example, according to the water-repellent chemical kit of the present invention or the method for producing a water-repellent fiber structure of the present invention, excellent oil repellency can be obtained, and it can be expected that, for example, sebum stains will not easily adhere to the fiber product. In general, non-fluorine-based water repellents have inferior oil repellency compared to fluorine-based water repellents, and sebum stains are easily adhered to the fiber product. However, according to the present invention, it is also possible to obtain a water-repellent fiber product with excellent oil repellency while using a non-fluorine-based water repellent.

The water-repellent chemical kit of the present invention or the method for producing a water-repellent fiber structure of the present invention can be used efficiently at low cost, and is excellent in water repellency, processing bath stability, storage stability, etc.

The textile structure that is the object to be treated by the water-repellent chemical kit of the present invention or the method for producing a water-repellent textile structure of the present invention is not particularly limited and may be any, for example, a textile product. The use of the water-repellent chemical kit of the present invention or the method for producing a water-repellent textile structure of the present invention is not particularly limited and may be widely applied to textile products such as clothing, umbrellas, raincoats, tent fabric, daily necessities, interior goods, car seats, and further to textile products such as water-repellent paper and water-repellent boards. Furthermore, the use of the water-repellent chemical kit of the present invention or the method for producing a water-repellent textile structure of the present invention is not limited to the above uses and may be widely used for any use.

The following describes examples of the present invention. Note that the present invention is not limited to these examples.

[Synthesis Example 1]
An adduct (b) of the components (b-1) and (b-2) was produced as follows, and further, an emulsion (dispersion) in which the adduct (b) was dispersed in water was obtained.

First, a reaction vessel was prepared. This reaction vessel was equipped with a stirrer with a Pfaudler blade, a reflux condenser, a thermometer, a nitrogen inlet tube, and a dropping funnel, and was capable of heating and cooling. Next, 67.1 parts by mass of stearyl isocyanate (component (b-2), 2.0% content of aliphatic groups having 17 or less carbon atoms) was placed in the reaction vessel. 14.9 parts by mass of polyvinyl alcohol copolymer (component (b-1), saponification degree 80%, average copolymerization degree 240) was further added as a raw polymer, and the mixture was stirred and dispersed. The mass ratio of the stearyl isocyanate (component (b-2)) and the polyvinyl alcohol copolymer (component (b-1)) was adjusted so that the molar ratio of isocyanate to hydroxyl groups was 1/1. The solution was further heated sufficiently to 50°C, and 17.7 parts by mass of dimethyl sulfoxide (hereinafter abbreviated as "DMSO") was added dropwise over about 60 minutes. Then, 0.1 parts by mass of 1,8 diazabicyclo[5,4,0]undecene-7 was added, stirred to dissolve, and the reaction was continued under sufficient stirring. The reaction was confirmed to be complete after stirring at about 50°C for about 60 minutes while checking the progress of the reaction. The progress of the reaction was checked by sampling the reaction solution appropriately and measuring the amount of the stearyl isocyanate compound in the reaction solution by infrared spectroscopy. After the reaction was completed, the reaction solution was cooled to 80°C, and the reaction mixture was poured into methanol in an amount 5 times the total amount of the reaction mixture, resulting in a white precipitate. Since the DMSO in the reaction solution dissolves in methanol, the DMSO can be removed from the white precipitate by filtration. Therefore, the white precipitate was separated by filtration, washed with methanol, dried, and then pulverized to obtain the target polymeric urethane compound (adduct (b) of components (b-1) and (b-2)).

10.5 parts by mass of the polymer urethane compound (adduct (b)) produced in this way, 1.3 parts by mass of LEOMIX 11 (hydrogenated tallow alkylamine acetate, cationic surfactant) manufactured by Lion Specialty Chemicals Co., Ltd., 2.0 parts by mass of NAA-45 (stearyl alcohol) manufactured by NOF Corporation, and 0.5 parts by mass of BROWNON 230 (polyoxyethylene stearyl ether (2E.O.), nonionic surfactant) manufactured by Aoki Oil & Fat Industries Co., Ltd. were placed in a container of a dispersing machine having an anchor mixer and sealed. After melting and mixing at 120°C, 85.7 parts by mass of hot water at 95°C or higher was mixed while maintaining the temperature at 110°C or higher and continuing to stir, and an emulsion (dispersion) in which the adduct (b) was dispersed in water was obtained.

[Example 1]
A water-repellent fiber structure was produced by the method for producing a water-repellent fiber structure of the present invention as described below.

First, the anionic polymer attachment process was carried out to attach the anionic polymer (A) to the fiber structure. A 100% nylon fabric or a 100% polyester fabric was used as the fiber structure. A batch method was used as the treatment method using the anionic polymer compound (A). Nylox 1500, a product name of Lion Specialty Chemicals Co., Ltd., was used as the anionic polymer (A). The weight ratio of the treatment bath by the exhaustion method was 1:20, the treatment temperature was 80°C, and the treatment time (immersion time) was 20 minutes. The amount of the anionic polymer compound (A) used was 8% o.w.f.

Furthermore, after the anionic polymer (A) was attached to the fiber structure, the excess anionic polymer (A) was removed by washing with water. Then, the fiber structure was allowed to dry naturally.

Next, the water-repellent treatment step was carried out in which the fiber structure to which the anionic polymer (A) was attached was treated with a non-fluorinated water-repellent agent (B) to make it water-repellent. That is, a treatment solution containing 6% by mass of the emulsion obtained in Synthesis Example 1 and 1% by mass of Elastron BN-11 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a blocked isocyanate was prepared, and the fiber structure after natural drying was immersed in this treatment solution (pickup rate 60% by mass).

Furthermore, the fiber structure after the water-repellent treatment step was dried at 130°C for 1 minute and further heat-treated at 170°C for 2 minutes to obtain the water-repellent fiber structure of Example 1. The water repellency and selective durable water repellency of the fabric thus obtained (water-repellent fiber structure) were evaluated by the method described below. The evaluation results are summarized in Table 4 described below.

[Example 2]
The water-repellent fiber structure of Example 2 was produced in the same manner as in Example 1, except that a continuous method was used instead of a batch method in the anionic polymer attachment treatment step. The continuous method was carried out as follows. As the fiber structure, a 100% nylon fabric or a 100% polyester fabric was used as in Example 1. As the anionic polymer (A), Nylox 1500 (trade name) manufactured by Lion Specialty Chemicals Co., Ltd. was used as in Example 1. A treatment solution was prepared using this, and the anionic polymer attachment treatment step was carried out by a continuous method through immersion treatment (pickup rate 60 mass%). Thereafter, the fiber structure was dried at 100°C for 1 minute to obtain a fiber structure to which the anionic polymer (A) was attached.

The water-repellent treatment step and the subsequent drying and heat treatment were carried out under the same conditions as in Example 1 to obtain a water-repellent fiber structure of Example 2. The water repellency and selective durable water repellency of the fabric thus obtained (water-repellent fiber structure) were evaluated by the method described below. The evaluation results are summarized in Table 4 described below.

[Comparative Example 1]
A water-repellent fiber structure of Comparative Example 1 was obtained in the same manner as in Example 1, except that the anionic polymer attachment treatment step was not performed. The water repellency and selective durable water repellency of the fabric (water-repellent fiber structure) thus obtained were evaluated by the methods described below. The evaluation results are summarized in Table 4 described below.

The water-repellent fiber structures of the examples and comparative examples manufactured as described above were tested and evaluated for water repellency when unwashed (0 washes) and after 20 washes (durable water repellency) using the following method.

[Water repellency evaluation method]
A water repellency test was carried out on each of the water repellent fiber structures (washed 0 times) of Example 1, Example 2, and Comparative Example 1 according to the spray method of JIS L 1092 (1998) at a shower water temperature of 23°C. The water repellency was visually evaluated on a scale of 0 to 5. The results are shown in Table 4.
Water repellency: Condition 5: No adhesion or wetting on the surface 4: Slight adhesion or wetting on the surface 3: Wetting on the surface 2: Wetting on the entire surface 1: Complete wetting on both sides 0: Complete wetting on both sides

[Durable water repellency evaluation method]
The water-repellent textile structures of Example 1, Example 2, and Comparative Example 1 were each washed 20 times (L-20) according to JIS L 1930 C4M. Thereafter, the water-repellent textile structures were subjected to a water-repellency test at a shower water temperature of 23°C according to the spray method of JIS L 1092 (1998) as in the above-mentioned "Water-repellency Evaluation Method". The water-repellency was evaluated visually on a scale of 0 to 5 as in the above-mentioned "Water-repellency Evaluation Method". The results are shown in Table 4 below.

As shown in Table 4, the fabrics (water-repellent fiber structures) of Examples 1 and 2 both had excellent water repellency before washing and after washing (also called durable water repellency or washing durability). In contrast, the water-repellent fiber structure of Comparative Example 1, to which the anionic polymer (A) was not attached, had water repellency before washing that was as high as that of Examples 1 and 2, but had inferior water repellency after washing compared to the Examples.

<Additional Notes>
A part or all of the above-described embodiments and examples may be described as follows, but are not limited to the following.

(Appendix 1)
an anionic polymer attachment treatment step of attaching an anionic polymer (A) to the fiber structure;
a water-repellent treatment step of subjecting the fiber structure to which the anionic polymer (A) is adhered to a water-repellent treatment with a non-fluorinated water-repellent agent (B);
A method for producing a water-repellent fiber structure, comprising:
(Appendix 2)
The method for producing a water-repellent fiber structure according to claim 1, wherein the anionic polymer (A) is at least one selected from the group consisting of polyhydric phenol condensates, polyhydric phenol condensate derivatives, phenolsulfonic acid-formalin polycondensates, thiophenol-formalin polycondensates, and bisphenol S sulfone-formalin polycondensates.
(Appendix 3)
The method for producing a water-repellent fiber structure according to claim 1 or 2, wherein the fiber structure is a polyester-based fiber structure or a nylon-based fiber structure.
(Appendix 4)
The method for producing a water-repellent fiber structure according to any one of Appendices 1 to 3, wherein the non-fluorinated water repellent (B) contains an adduct (b) of the following components (b-1) and (b-2):
(b-1) a vinyl polymer having at least one substituent selected from the group consisting of a hydroxyl group, an amino group, and an imino group; (b-2) an isocyanate having an aliphatic group having 8 or more carbon atoms (Appendix 5);
The method for producing a water-repellent fiber structure according to any one of Appendices 1 to 4, wherein the mass of fluorine as an element contained in the non-fluorine water repellent (B) is 1 mass% or less, with the total mass of the non-fluorine water repellent (B) being 100 mass%.
(Appendix 6)
A water-repellent treatment agent kit for a textile structure, comprising an anionic polymer (A) and a non-fluorinated water repellent agent (B).
(Appendix 7)
The water-repellent treatment chemical kit according to claim 6, wherein the anionic polymer (A) is at least one selected from the group consisting of polyhydric phenol condensates, phenolsulfonic acid-formalin polycondensates, thiophenol-formalin polycondensates, and bisphenol S sulfone-formalin polycondensates.
(Appendix 8)
The water-repellent treatment agent kit according to claim 6 or 7, wherein the fiber structure is a polyester-based fiber structure or a nylon-based fiber structure.
(Appendix 9)
The water-repellent agent kit according to any one of Appendices 6 to 8, wherein the non-fluorinated water repellent (B) contains an adduct (b) of the following components (b-1) and (b-2):
(b-1) a vinyl polymer having at least one substituent selected from the group consisting of a hydroxyl group, an amino group, and an imino group; (b-2) an isocyanate having an aliphatic group having 8 or more carbon atoms (Appendix 10);
The water-repellent agent kit according to any one of Appendices 6 to 9, wherein the mass of fluorine as an element contained in the non-fluorine water repellent agent (B) is 1 mass% or less, with the total mass of the non-fluorine water repellent agent (B) being 100 mass%.

Claims (5)

an anionic polymer attachment treatment step of attaching an anionic polymer (A) to the fiber structure;
a water-repellent treatment step of subjecting the fiber structure to which the anionic polymer (A) is adhered to a water-repellent treatment with a non-fluorinated water-repellent agent (B);
A method for producing a water-repellent fiber structure, comprising: The method for producing a water-repellent fiber structure according to claim 1, wherein the anionic polymer (A) is at least one selected from the group consisting of polyhydric phenol condensates, polyhydric phenol condensate derivatives, phenolsulfonic acid-formalin polycondensates, thiophenol-formalin polycondensates, and bisphenol S sulfone-formalin polycondensates. The method for producing a water-repellent fiber structure according to claim 1 or 2, wherein the fiber structure is a polyester-based fiber structure or a nylon-based fiber structure. 3. The method for producing a water-repellent fiber structure according to claim 1, wherein the non-fluorinated water repellent (B) comprises an adduct (b) of the following components (b-1) and (b-2):
(b-1) a vinyl polymer having at least one substituent selected from the group consisting of a hydroxyl group, an amino group, and an imino group; and (b-2) an isocyanate having an aliphatic group having 8 or more carbon atoms. A water-repellent treatment chemical kit for textile structures, comprising an anionic polymer (A) and a non-fluorinated water repellent agent (B).