JP2021075607A - Water-repellent composition, water-repellent fiber product and method for producing water-repellent fiber product - Google Patents

Abstract

To provide a fluorine-free water-repellent composition that can give a fiber product having excellent water repellency and durable water repellency and having a good texture.SOLUTION: A water-repellent composition contains a resin (A) that is a reactant of a polyamine (a1) having a secondary amino group, a C10-36 monocarboxylic acid (a2) and epihalohydrin (a3-1) or glycidol (a3-2), and silicone (B). A mass ratio between the resin (A) and the silicone (B), ((A)/(B)), is more than 1 to less than 99 in terms of solid content.SELECTED DRAWING: None

Description

The present invention relates to a water repellent composition, a water repellent fiber product, and a method for producing a water repellent fiber product.

Conventionally, a fluorine-based water repellent is known as a water-repellent agent used for fibers, and a fiber whose surface is imparted with water repellency by treating a textile product or the like with such a fluorine-based water repellent. The product is known. Such a fluorine-based water repellent is generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group.

However, although textile products treated with a fluorine-based water repellent exhibit excellent water repellency, monomers having a fluoroalkyl group are not economically satisfactory because they are expensive, and further. Since the monomer having a fluoroalkyl group is persistently decomposable, there is a problem in terms of the environment.

Therefore, in recent years, research has been conducted on non-fluorine-based water repellents that do not contain fluorine. For example, Patent Document 1 proposes a water-repellent agent obtained by emulsifying and dispersing a specific non-fluoropolymer, and Patent Document 2 describes a silicone-based water repellent composition containing a polyorganosiloxane and a metal alkoxide. Proposed.

Japanese Unexamined Patent Publication No. 2006-328624 Japanese Unexamined Patent Publication No. 7-305053

However, the textile products treated with the non-fluorine-based water repellent described in Patent Document 1 are still insufficient in water repellency in terms of practical use, and further, water repellency (durable water repellency) in the textile products after washing. Was not satisfactory. Further, the silicone-based water repellent agent as in Patent Document 2 has a problem that many of the textile products treated with the silicone-based water repellent have an insufficient texture.

An object of the present invention is to provide a non-fluorine-based water repellent composition capable of providing a textile product having excellent water repellency and durable water repellency and having a good texture.

As a result of diligent studies to solve the above problems, the present inventor has made a water repellent composition containing a specific resin and silicone which are reactants of a predetermined polyamine, monocarboxylic acid and epihalohydrin or glycidol in a specific mass ratio. The present invention was completed by finding that the above problems can be solved. That is, the present invention relates to the following water repellent composition.

A polyamine (a1) having a 1.2-grade amino group, a resin (A) which is a reaction product of a monocarboxylic acid (a2) having 10 to 36 carbon atoms and epihalohydrin (a3-1) or glycidol (a3-2), and a resin (A). , Contains silicone (B),
A water repellent composition having a mass ratio ((A) / (B)) of the resin (A) and the silicone (B) of more than 1 and less than 99 in terms of solid content.

2. The component (a1) is the general formula (1): H ₂ N-[(CH ₂ ) _m NH] _n- H (in the formula, m represents an integer of 1 to 6 and n represents an integer of 2 to 6). Item 2. The water repellent composition according to Item 1, which is a compound represented by.

3. 3. Item 2. The water repellent composition according to Item 1 or 2, wherein the component (a2) is an aliphatic monocarboxylic acid having 16 to 24 carbon atoms.

4. The water repellent composition according to any one of Items 1 to 3 above, wherein the component (a3-1) is epichlorohydrin.

5. The water repellent composition according to any one of Items 1 to 4, wherein the component (B) is a long-chain alkyl group-containing silicone and / or a silicone resin.

6. The water repellent composition according to any one of Items 1 to 5, wherein (A) / (B) is 3 to 9 in terms of solid content.

7. A water-repellent fiber product containing the fiber and the water-repellent composition according to any one of Items 1 to 6 above.

8. A method for producing a water-repellent fiber product, which comprises a step of treating the fiber with a treatment liquid containing the water-repellent composition according to any one of the above items 1 to 6.

The water repellent composition of the present invention can impart excellent water repellency and durable water repellency to textile products as compared with conventional non-fluorinated water repellents, and the textile products also have a good texture. ..

[Water repellent composition]
In the present invention, a polyamine (a1) having a secondary amino group (hereinafter referred to as (a1) component), a monocarboxylic acid (a2) having 10 to 36 carbon atoms (hereinafter referred to as (a2) component) and epihalohydrin (hereinafter referred to as (a2) component) ( Resin (A) (hereinafter referred to as (A)) which is a reaction product of a3-1) (hereinafter referred to as (a3-1) component) or glycidol (a3-2) (hereinafter referred to as (a3-2) component). The solid content is the mass ratio ((A) / (B)) of the component (A) and the component (B), which contains (referred to as a component) and silicone (B) (hereinafter referred to as the component (B)). It relates to a water repellent composition having a conversion of more than 1 and less than 99.

<Resin (A)>
The component (a1) is not particularly limited as long as it has a secondary amino group, and various known components can be used. The component (a1) may have a primary amino group and a tertiary amino group in its molecule. As the component (a1), one type can be used alone, or two or more types can be used in combination.

The component (a1) is, for example, the general formula (1): H ₂ N-[(CH ₂ ) _m NH] _n- H (in the formula, m is an integer of 1 to 6 and n is an integer of 2 to 6). ), And the like. As the component (a1), it is preferable to use a compound represented by the general formula (1).

Examples of the compound represented by the general formula (1) include polyalkylene polyamines and the like. Examples of the polyalkylene polyamine include polyethylene polyamine and polypropylene polyamine.

Examples of the polyethylene polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like. Examples of the polypropylene polyamine include dipropylene triamine, tripropylene tetramine, tetrapropylene pentamine, and pentapropylene hexamine.

As the component (a1), diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are easily available as general-purpose industrial reagents, are easy to handle as a liquid having a low viscosity at room temperature, and are preferable from the viewpoint of stable supply.

The component (a2) is not particularly limited as long as it is a monocarboxylic acid having 10 to 36 carbon atoms, and various known components can be used. As the component (a2), one type can be used alone, or two or more types can be used in combination.

Examples of the component (a2) include aromatic monocarboxylic acids having 10 to 36 carbon atoms and aliphatic monocarboxylic acids having 10 to 36 carbon atoms.

Examples of the aromatic monocarboxylic acid having 10 to 36 carbon atoms include toluic acid and naphthalene carboxylic acid. Further, the aromatic monocarboxylic acid may have a substituent such as an alkyl group or an alkenyl group having 1 to 12 carbon atoms.

Examples of the above-mentioned aliphatic monocarboxylic acid having 10 to 36 carbon atoms include saturated fatty acids having 10 to 36 carbon atoms, unsaturated fatty acids having 10 to 36 carbon atoms, and vegetable fats and oils having 10 to 36 carbon atoms. Examples thereof include fatty acids derived from animal fats and oils and their anhydrides. Further, the aliphatic monocarboxylic acid having 10 to 36 carbon atoms may be used as a halide such as acid chloride in order to facilitate the reaction.

Examples of the saturated fatty acid include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and melissic acid.

Examples of the unsaturated fatty acid include palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, gadoleic acid, arachidonic acid and the like.

Examples of the fatty acids derived from the above-mentioned vegetable fats and oils or animal fats and oils include coconut oil fatty acids, coconut oil fatty acids, palm oil fatty acids, beef fat fatty acids, soybean oil fatty acids, rapeseed oil fatty acids, and tall oil fatty acids.

The component (a2) is preferably an aliphatic monocarboxylic acid having 10 to 36 carbon atoms from the viewpoint of excellent water repellency and durable water repellency of the textile product and excellent reactivity with the component (a1). Further, from the same point of view, the component (a2) is more preferably an aliphatic monocarboxylic acid having 16 to 24 carbon atoms.

The component (a3-1) is not particularly limited as long as it is epihalohydrin, and various known components can be used. As the component (a3-1), one type can be used alone, or two or more types can be used in combination.

Examples of the component (a3-1) include epichlorohydrin, epibromohydrin, epiiodohydrin, methylepichlorohydrin and the like. The component (a3-1) is preferably epichlorohydrin because it is inexpensive and easy to handle.

The component (a3-2) is not particularly limited as long as it is glycidol, and various known components can be used. As the component (a3-2), one type can be used alone, or two or more types can be used in combination.

Examples of the component (a3-2) include 2,3-epoxy-1-propanol, 3,4-epoxy-1-butanol and the like.

<Physical characteristics and manufacturing method of resin (A)>
The amount of the component (a1), the component (a2) and the component (a3-1) or the component (a3-2) used in the component (A) is not particularly limited.

The amount of the component (a1) and the component (a2) used in the component (A) is as follows, assuming that the number of primary amino groups contained in the component (a1) is M and the number of secondary amino groups is N. The amount of the component (a2) is preferably about (M) to (M + 0.9N) mol with respect to 1 mol of the a1) component. When the amount of the component (a2) used is (M) mol or more, it tends to be superior to the water repellency and durable water repellency of the textile product, and when it is (M + 0.9N) mol or less, the component (A) Will be more stable. When the component (a1) is a mixture of a plurality of polyamines, M needs to be an average value.

The amount of the component (a3-1) or the component (a3-2) used in the component (A) is 0. It is preferably about 1N to 1.5N mol, more preferably about 0.3N to 0.75N mol. N is the same as above.

The method for producing the component (A) is not particularly limited as long as it is a method for reacting the component (a1), the component (a2) and the component (a3-1) or the component (a3-2), and various known production methods can be used. Illustrated. Specifically, for example, the component (a1) and the component (a2) are heated to 150 ° C. or higher, reacted for about 2 to 8 hours while removing the by-produced water, and then dissolved in a solvent or water. Alternatively, a method of dispersing and adding the component (a3-1) or the component (a3-2) and reacting for about 2 to 6 hours can be mentioned. In the above reaction, when it is difficult to disperse the reactants from the component (a1) and the component (a2), the mixture may be heated in the range of 40 ° C. or higher and 120 ° C. or lower, or an emulsifying dispersant may be used in combination. Is also good.

The form of the component (A) is not particularly limited. The component (A) may be used as it is, or may be used as a solution or a dispersion liquid dissolved or dispersed (including suspension and emulsification) in a solvent or water. The component (A) is preferably an aqueous dispersion.

The method for preparing the aqueous dispersion of the component (A) is not particularly limited, and various known methods can be used. Specifically, for example, a method of dispersing the component (A) in water in the presence or absence of an emulsifier; a method of using the dispersion liquid of the component (A) obtained in the presence of water as it is in the above production method. Alternatively, a method using a commercially available product of the aqueous dispersion of the component (A) can be mentioned.

The above dispersion method is not particularly limited. Examples of the dispersion method include a mechanical emulsification method in which the component (A) and water are forcibly emulsified, and an inversion method in which water is gradually added to the melt of the component (A) to invert the oil phase and the aqueous phase. Examples include an emulsification method, a high-pressure emulsification method in which the component (A) and water are emulsified under high pressure. The emulsifying machine used in the above mechanical emulsification method is not particularly limited, and examples thereof include a homomixer, a high-pressure homogenizer (manufactured by Menton-Gaulin), and a ball mill.

The emulsifier is not particularly limited and various known emulsifiers can be used. Examples of the emulsifier include cationic surfactants, nonionic surfactants, reactive emulsifiers and the like. The amount of the emulsifier used is usually in the range of about 1 to 10% by mass in terms of solid content with respect to the component (A).

Examples of the cationic surfactant include tetraalkylammonium chloride, trialkylbenzylammonium chloride, alkylamine acetate, alkylamine hydrochloride, oxyethylenealkylamine, polyoxyethylenealkylamine, alkylamine acetate, and cationized starch. Can be mentioned. The cationized starch is, for example, selected from the group consisting of primary, secondary, tertiary amino groups and quaternary ammonium groups in raw starch such as corn, potato, tapioca, wheat and rice. Examples thereof include those in which one kind of basic nitrogen group is incorporated into a molecule.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, sorbitan higher fatty acid esters, polyoxyethylene sorbitan higher fatty acid esters, and polyoxy. Examples thereof include ethylene higher fatty acid esters, glycerin higher fatty acid esters, and block copolymers of polyalkylene oxides. Specific examples thereof include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene nonylphenyl ether, and polyoxyethylene. Styrylphenyl ether, sorbitan monolaurate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene monolaurate, polyoxyethylene monooleate, oleic acid monoglyceride, stearate monoglyceride, polyoxyethylene polyoxypropylene -Examples include block copolymers.

The reactive emulsifier is not particularly limited as long as it is an emulsifier having a functional group containing a double bond capable of radical polymerization, and various known emulsifiers can be used. Examples of the double bond capable of radical polymerization include a (meth) acryloyl group and an allyl group.

Examples of the reactive emulsifier include a polyoxyethylene alkyl ether having at least one functional group containing a double bond capable of radical polymerization in the molecule, and a polyoxyethylene alkyl having at least one functional group in the molecule. Sulfosuccinic acid ester salt of ether, sulfate ester salt of polyoxyethylene alkyl ether having at least one functional group in the molecule, polyoxyethylene phenyl ether having at least one functional group in the molecule, molecular of the functional group. A sulfosuccinate salt of polyoxyethylene phenyl ether having at least one in the molecule, a sulfate ester salt of polyoxyethylene phenyl ether having at least one functional group in the molecule, and a poly having at least one functional group in the molecule. Oxyethylene alkylphenyl ether, sulfosuccinate salt of polyoxyethylene alkylphenyl ether having at least one functional group in the molecule, sulfate ester salt of polyoxyethylene alkylphenyl ether having at least one functional group in the molecule , Polyoxyethylene aralkylphenyl ether having at least one functional group in the molecule, sulfosuccinate salt of polyoxyethylene aralkylphenyl ether having at least one functional group in the molecule, at least the functional group in the molecule. Sulfate ester salt of polyoxyethylene aralkylphenyl ether having one, phosphate ester salt of polyoxyethylene alkylphenyl ether having at least one functional group in the molecule, poly having at least one functional group in the molecule An aliphatic or aromatic carboxylate of oxyethylene alkylphenyl ether, an acidic phosphoric acid (meth) acrylic acid ester-based emulsifier, an acid anhydride-modified product of rosing lysidyl ester acrylate (see JP-A-4-256429), JP-A. Examples thereof include various substances such as emulsifiers described in JP-A-63-23725, JP-A-63-240931, and JP-A-62-104802.

Further, the polyoxyethylene in the above-mentioned reactive emulsifier may be replaced with polyoxypropylene or a block copolymerization or random copolymerization of polyoxypropylene and polyoxypropylene. Examples of these commercially available products include KAYAMER PM-1, KAYAMER PM-2, KAYAMER PM-21 (all manufactured by Nippon Kayaku Co., Ltd.), SE-10N, NE-10, NE-20, and NE. -30, Adecaria Soap SR-10, Adecaria Soap SR-20, Adecaria Soap ER-20 (above, manufactured by ADEKA Corporation), New Frontier A229E, New Frontier N117E, New Frontier N250Z, Aqualon RN-10, Aqualon RN-20, Aqualon RN-50, Aqualon HS-10, Aqualon KH-05, Aqualon KH-10 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Eleminor JS-2 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) , Latemul K-180 (manufactured by Kao Corporation) and the like are typical examples.

As the emulsifier, it is preferable to use a cationic surfactant or a nonionic surfactant.

If necessary, a protective colloid may be used. The protective colloid is not particularly limited and known ones can be used. Specifically, for example, those obtained by polymerizing an anionic monomer, a cationic monomer and other monomers can be mentioned. The anionic monomer has at least one anionic functional group and one vinyl group, and specifically, for example, a monocarboxylic acid such as (meth) acrylic acid and crotonic acid; maleic acid and fumaric acid. , Dicarboxylic acids such as itaconic acid, muconic acid, citraconic acid; organic sulfonic acids such as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid, (meth) allyl sulfonic acid; or various organic acids thereof. Examples include sodium salt and potassium salt. The cationic monomer has at least one cationic functional group and one vinyl group, and specifically, for example, in addition to allylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N. -Vinyl monomers having a tertiary amino group such as diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, or their hydrochloric acid, sulfuric acid, acetic acid, etc. Contains salts of inorganic or organic acids, or quaternary ammonium salts obtained by reacting the tertiary amino group-containing vinyl monomer with a quaternizing agent such as methyl chloride, benzyl chloride, dimethyl sulfate, or epichlorohydrin. Examples include vinyl monomers. Examples of the monomer other than the anionic monomer and the cationic monomer include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, and the like. N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-t-butyl (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) ) Acrylate alkyl esters such as butyl acrylate, allyl-based monomers containing an allyl group such as allyl alcohol, N-substituted acrylamide-based monomers such as isopropylacrylamide, (meth) acrylonitrile, and other bifunctional vinyl monomers. As a system, bisacrylamide-based monomers such as methylenebis (meth) acrylamide and ethylenebis (meth) acrylamide, diacrylate-based monomers such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, diallylamine, divinylbenzene, etc. Examples of polyfunctional vinyl monomers having 3 or more vinyl groups include 1,3,5-triacloylhexahydro-S-triazine, triallyl isocyanurate, triallylamine, tetramethylolmethanetetraacrylate and the like. .. The polymerization method may be a known method such as a radical polymerization method.

The amount of the protective colloid used in the aqueous dispersion of the component (A) is not particularly limited, but is preferably about 1 to 10 parts by mass with respect to 100 parts by mass of the component (A).

The physical characteristics of the aqueous dispersion of the component (A) are not particularly limited. The concentration of the aqueous dispersion of the component (A) is preferably about 0.1 to 50% by weight in terms of solid content in consideration of workability and the like. Further, the aqueous dispersion of the component (A) preferably has a volume average particle diameter of about 0.2 to 10 μm in consideration of its dispersibility. Further, the aqueous dispersion of the component (A) preferably has a pH of about 3 to 7, and its appearance is usually white to yellowish white.

For the component (A), the number of secondary amino groups present in the component (a1) present therein is x, and the secondary amino group of the component (a1) and the component (a3-1) or (a3-2) ) When the number of tertiary amino groups generated by the reaction of the components is y, the value of y / x is more preferably 0.1 to 0.95. When the value of z / y is in the above range, it becomes superior to the water repellency and the durable water repellency in the textile product. The component (A) preferably has a y / x value of about 0.2 to 0.9, preferably 0.2 to 0.7, from the viewpoint of excellent water repellency and durable water repellency of the textile product. Is particularly preferable.

<Silicone (B)>
The component (B) is not particularly limited, and various known components can be used. As the component (B), one type may be used alone or two or more types may be used in combination.

Examples of the component (B) include silicone resin and silicone oil.

(Silicone resin)
The silicone resin is not particularly limited. The silicone resin contains, for example, T units and / or Q units as constituents, and at least one siloxane unit selected from M units and D units as constituent units other than the T units and / or Q units. , Organopolysiloxane having a three-dimensional structure. The M unit, D unit, T unit, and Q unit _{mean (R) 3} SiO _1/2 unit, (R) ₂ SiO _2/2 unit, RSiO _3/2 unit, and SiO _4/2 unit, respectively. ..

The R in the M unit, D unit, T unit and Q unit is hydrolyzable independently of each other, substituted or unsubstituted, monovalent hydrocarbon group having 1 to 12 carbon atoms, hydroxyl group, and 1 to 6 carbon atoms. Groups and the like are exemplified.

Examples of the monovalent hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group and 2-ethylhexyl. Alkyl group such as group, nonyl group, decyl group, dodecyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl Alkenyl groups such as groups; aryl groups such as phenyl group, trill group, xsilyl group, α-, β-naphthyl group; aralkyl groups such as benzyl group, 2-phenylethyl group and 3-phenylpropyl group; or these A group in which a part or all of the hydrogen atom of the group is substituted with a halogen atom such as F, Cl, Br, or a cyano group (for example, 3-chloropropyl group, 3,3,3-trifluoropropyl group, 2). -Cyanoethyl group, etc.).

Examples of the hydrolyzable group include a methoxy group and an alkoxy group such as an ethoxy group.

The silicone resin is, for example, an MQ resin containing the M units and the Q units as main components, a TD resin containing the T units and the D units as main components, and an MT resin containing the M units and T units as main components. The MDQ resin consisting of the M unit, the D unit and the Q unit, the MDT resin consisting of the M unit, the D unit and the T unit, and the MDTQ resin consisting of the M unit, the D unit, the T unit and the Q unit, etc. Can be mentioned.

Commercially available products of the above silicone resin include, for example, KS-3800, KF-7312J, KF-7312F, KF-9021L, KF-7312L, X-92-183, KM-9717, X-52-8005, X-51. -1302M (all manufactured by Shin-Etsu Chemical Co., Ltd.), SD-7292, BY24-843, MQ-1600, MQ-1640 (all manufactured by Toray Dow Corning Co., Ltd.) and the like.

(Silicone oil)
The silicone oil is not particularly limited. Examples of the silicone oil include linear organopolysiloxane. Examples of the organopolysiloxane include those having an organic group at at least one of its side chain and its terminal.

Examples of the silicone oil include straight silicone and modified silicone.

Examples of the straight silicone include dimethyl silicone, methyl phenyl silicone, and methyl hydrogen silicone.

The modified silicones include, for example, amino group-containing silicones, epoxy group-containing silicones, carbinol group-containing silicones, mercapto group-containing silicones, carboxyl group-containing silicones, polyether group-containing silicones, long-chain alkyl group-containing silicones, and aralkyl group-containing silicones. , Long-chain alkyl / aralkyl group-containing silicone, higher fatty acid ester group-containing silicone, higher aliphatic amide group-containing silicone, and the like.

Examples of the amino group-containing silicone include compounds having an organic group containing an amino group and / or an imino group at at least one of the side chain and the terminal of the siloxane structure. Commercially available products of amino group-containing silicone include, for example, WACKER FINISH WR301, WR1100, WR1200, WR1300, WR1600 (all manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), KF8005, KF-868, KF-864, KF-393, KF-8021 ( Above, Shin-Etsu Chemical Co., Ltd.), TSF-4709, XF42-B1989 (above, manufactured by Momentive Performance Materials Japan (joint)), BY16-872, SF-8417, BY16-853U, BY16-892 (The above is manufactured by Toray Dow Corning Co., Ltd.) and the like.

Examples of the epoxy group-containing silicone include compounds having an organic group containing an epoxy group at at least one of the side chain and the terminal of the siloxane structure. Commercially available products of epoxy group-containing silicone include, for example, X-22-343, KF-101, KF-1001, X-22-163, X-22-163A, X-22-163B, X-22-163C, KF. -105, X-22-169AS, X-22-169B, X-22-173BX, X-22-173DX (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like can be mentioned.

Examples of the carbinol group-containing silicone include compounds having an organic group containing a carbinol group in at least one of the side chain and the terminal of the siloxane structure. Commercially available products of carbinol group-containing silicone include, for example, X-22-2439, X-22-4015, X-22-170BX, X-22-170DX, KF-6000, KF-6001, KF-6002, KF- 6003 (above, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned.

Examples of the mercapto group-containing silicone include compounds having an organic group containing a mercapto group at at least one of the side chain and the terminal of the siloxane structure. Examples of commercially available products of mercapto group-containing silicone include KF-2001, KF-2004, X-22-167B, and X-22-167C (all manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of the carboxyl group-containing silicone include compounds having an organic group containing a carboxyl group at at least one of the side chain and the terminal of the siloxane structure. Examples of commercially available carboxyl group-containing silicone products include X-22-3701E and X-22-162C (all manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of the above-mentioned polyether group-containing silicone include compounds having an organic group containing a polyether group at at least one of the side chain and the terminal of the siloxane structure. Examples of the polyether group include a polyoxyethylene group, a polyoxypropylene group, and a polyoxyalkylene group having a block structure of polyoxyethylene / polyoxypropylene. Commercially available products of the polyether group-containing silicone include, for example, SF8410 (manufactured by Toray Dow Corning Co., Ltd.), KF-6004, KF-6011, KF-6012, KF-6020, KF-6204, X-22-4515 ( As mentioned above, Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned.

Examples of the long-chain alkyl group-containing silicone include compounds having an organic group containing a long-chain alkyl group in at least one of the side chain and the terminal of the siloxane structure. The long-chain alkyl group is not particularly limited, but an alkyl group having 6 or more carbon atoms is preferable, and an alkyl group having 6 to 36 carbon atoms is more preferable, from the viewpoint of excellent water repellency and durable water repellency of the textile product. Commercially available long-chain alkyl group-containing silicones include, for example, SF8416 (manufactured by Toray Dow Corning Co., Ltd.), KF-421, KF-413, KF-414, KF-415, KF-4003, KF-4701, KF. -4917, KF-7235B, X-22-1877, X-52-8046 (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned.

Examples of the aralkyl group-containing silicone include compounds having an organic group containing an aralkyl group in at least one of the side chain and the terminal of the siloxane structure. Examples of the aralkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group and the like. Examples of commercially available products of aralkyl group-containing silicone include KF-410 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of the long-chain alkyl-aralkyl group-containing silicone include compounds having the long-chain alkyl group and an organic group containing the aralkyl group in at least one of the side chain and the terminal of the siloxane structure. Examples of commercially available long-chain alkyl-aralkyl group-containing silicone products include SH203 (manufactured by Toray Dow Corning Co., Ltd.) and X-22-1877 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of the higher fatty acid ester group-containing silicone include compounds having an organic group containing a higher fatty acid ester group in at least one of the side chain and the terminal of the siloxane structure. Examples of commercially available products of higher aliphatic ester group-containing silicones include X-22-715 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of the higher aliphatic amide group-containing silicone include compounds having an organic group containing the higher aliphatic amide group at at least one of the side chain and the terminal of the siloxane structure. Examples of commercially available products of higher aliphatic amide group-containing silicones include KF-3935 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The component (B) is preferably a silicone resin, a long-chain alkyl group-containing silicone, an aralkyl group-containing silicone, or a long-chain alkyl / aralkyl group-containing silicone from the viewpoint of excellent water repellency and durable water repellency of the textile product, and from the same viewpoint. , MQ resin, long-chain alkyl group-containing silicone is more preferable.

The form of the component (B) is not particularly limited. The component (B) may be used as it is, or may be used as a solution or a dispersion liquid dissolved or dispersed (including suspension and emulsification) in a solvent or water. The component (B) is preferably an aqueous dispersion.

The method for producing the aqueous dispersion of the component (B) is not particularly limited, but for example, a method of dispersing the component (B) in water in the presence or absence of an emulsifier; Examples include a method of using a product. The above-mentioned dispersion method and emulsifier are not particularly limited, and examples thereof include the same as those described above.

<Additives>
The water repellent composition may contain various known additives, if necessary, as long as the effects of the present invention are not impaired. Additives include, for example, water repellents other than the above water repellent composition, surfactants, defoamers, pH adjusters, antibacterial agents, fungicides, colorants, antioxidants, deodorants, and various organic substances. Examples thereof include solvents, chelating agents, antistatic agents, catalysts, cross-linking agents described later, antibacterial deodorants, flame retardants, softeners, and anti-wrinkle agents. The above additives can be used alone or in combination of two or more.

Examples of the defoaming agent include fat-based defoaming agents such as castor oil, sesame oil, flaxseed oil, and animal and vegetable oils; fatty acid-based defoaming agents such as stearic acid, oleic acid, and palmitic acid; Fatty acid ester defoamers such as stearyl, ethylene glycol distearate, butyl stearate; alcoholic defoamers such as polyoxyalkylene monohydric alcohol di-t-amylphenoxyethanol, 3-heptanol, 2-ethylhexanol; Di-t-amylphenoxyethanol 3-heptyl cellosolve nonyl cellosolve 3-ether-based defoamers such as heptyl carbitol; phosphate ester-based defoamers such as tributyl osphate and tris (butoxyethyl) fuosphate; amine-based defoamers such as diamilamine Examples thereof include defoaming agents; amide-based defoaming agents such as polyalkyleneamide and acylate polyamine; sulfuric acid ester-based defoaming agents such as sodium lauryl sulfate; mineral oil and the like. The defoaming agent may be used alone or in combination of two or more.

Examples of the pH adjusting agent include organic acids such as lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, citric acid, malic acid, sulfonic acid, methanesulfonic acid and toluenesulfonic acid; hydrochloric acid, sulfuric acid, nitrate and phosphoric acid. , Inorganic acids such as boric acid; bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia, alkanolamine, pyridine, morpholin and the like. The pH adjuster may be used alone or in combination of two or more.

Examples of the organic solvent include aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, hexyl alcohol, and 2-ethylhexyl alcohol; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone. , Ketones such as diacetone alcohol; esters such as ethyl acetate, methyl acetate, butyl acetate, methyl lactate, ethyl lactate; diethyl ether, diisopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, dioxane, methyl tertiary butyl ether, butyl Ethers such as carbitol; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol; ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether Glycol ethers such as 3-methoxy-3-methyl-1-butanol; glycol esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate; formamide, acetamide, benzamide, N, N -Amids such as dimethylformamide and acetanilide can be mentioned. As the organic solvent, one type can be used alone or two or more types can be used in combination.

As the antistatic agent, it is preferable to use an antistatic agent that does not easily impair the water repellency. Antistatic agents include, for example, cationic surfactants such as higher alcohol sulfates, sulfated oils, sulfonates, quaternary ammonium salts, imidazoline type quaternary salts, polyethylene glycol type, polyhydric alcohol ester type. Nonionic surfactants such as, imidazoline type quaternary salts, amphoteric surfactants such as alanine type and betaine type, polymer compound type antistatic polymers, polyalkylamines and the like can be mentioned. The antistatic agent may be used alone or in combination of two or more.

[Physical characteristics and manufacturing method of water repellent composition]

The physical characteristics of the water repellent composition are not particularly limited. The concentration of the water repellent composition is preferably about 0.1 to 50% by weight in terms of solid content in consideration of workability and the like. Further, the water repellent composition preferably has a volume average particle size of about 0.2 to 10 μm in consideration of its dispersibility. Further, the pH of the water repellent composition is preferably about 3 to 7, and the appearance of the water repellent composition is usually white to yellowish white.

The water repellent composition has a mass ratio ((A) / (B)) of the component (A) to the component (B) of more than 1 and less than 99 in terms of solid content. When the mass ratio is 1 or less, the texture of the textile product is insufficient. When the mass ratio is 99 or more, the water repellency and durable water repellency of the textile product are lowered. The mass ratio is preferably about 3 to 9 in terms of solid content from the viewpoint of excellent balance of water repellency, durable water repellency and texture in textile products.

The content of the component (A) in the water repellent composition is not particularly limited, but from the viewpoint of excellent water repellency, durable water repellency and texture in the textile product, the content of the component (A) is relative to 100% by mass of the water repellent composition. It is preferably about 60 to 97% by mass in terms of solid content.

The content of the component (B) in the water repellent composition is not particularly limited, but from the viewpoint of excellent water repellency, durable water repellency and texture in the textile product, the content of the component (B) is based on 100% by mass of the water repellent composition. It is preferably about 3 to 40% by mass in terms of solid content.

The method for producing the water repellent composition of the present invention is not particularly limited, and various known methods can be used. Specifically, for example, a method of mixing the component (A) and the component (B), and if necessary, the above-mentioned additive can be mentioned. The mixing order of each component is not particularly limited, and any component may be mixed first. Further, the mixing method is not particularly limited, and various known methods such as stirring can be used.

[Water-repellent textile products]
The water-repellent fiber product of the present invention can be obtained by treating the fiber with a treatment liquid containing the water-repellent composition.

(Treatment liquid)
As the treatment liquid, the water repellent composition may be used as it is as a treatment liquid, or may be further diluted with an aqueous medium or a hydrophobic solvent to prepare a treatment liquid.

The aqueous medium is preferably, for example, water or a mixed solvent of water and a hydrophilic solvent mixed with water. Examples of the hydrophilic solvent include methanol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, hexylene glycol, glycerin (1, butyl glycol, butyl diglycol, solfit, N-methylpyrrolidone, dimethylformamide, dimethylsulfooxide and the like. Can be mentioned.

(Crosslinking agent)
The treatment liquid may further contain a cross-linking agent for the purpose of improving the durable water repellency of the water-repellent fiber product. Examples of the cross-linking agent include a melamine resin, a compound having one or more isocyanate groups or blocked isocyanate groups, and the like.

As the melamine resin, a compound having a melamine skeleton can be used. For example, polymethylol melamine such as trimethyl melamine and hexamethylol melamine; a part or all of the methylol groups of the methylol melamine have 1 to 6 carbon atoms. Amethylmethylmelamine that has become an alkoxymethyl group having an alkyl group; asyloxymethylmelamine in which a part or all of the methylol group of polymethylol melamine has become an acyloxymethyl group having an acyl group having 2 to 6 carbon atoms. Can be mentioned. These melamine resins may be either monomers, dimers or more multimers, or mixtures thereof. Further, a product obtained by copolymerizing a part of melamine with urea or the like can also be used. Examples of such melamine resins include Beccamin APM, Beccamin M-3, Beccamin M-3 (60), Beccamin MA-S, Beccamin J-101, and Beccamin J-101LF manufactured by DIC Corporation. Examples include Unica Resin 380K manufactured by Miki Riken Kogyo Co., Ltd. and Riken Resin MM series manufactured by Miki Riken Kogyo Co., Ltd.

It is preferable to use a catalyst for the melamine resin from the viewpoint of accelerating the reaction. Such a catalyst is not particularly limited as long as it is a commonly used catalyst, and is, for example, a borofluorinated compound such as ammonium borofluoride or subsalt borofluoride; a neutral metal salt catalyst such as magnesium chloride or magnesium sulfate. ; Examples include inorganic acids such as phosphoric acid, hydrochloric acid, and boric acid. If necessary, organic acids such as citric acid, tartaric acid, malic acid, maleic acid, and lactic acid can be used in combination with these catalysts. Examples of such a catalyst include Catalyst ACX, Catalyst 376, Catalyst O, Catalyst M, Catalyst G (GT), Catalyst X-110, Catalyst GT-3, and Catalyst GT-3 manufactured by DIC Corporation. Catalyst NFC-1, Unica Catalyst 3-P manufactured by Union Chemical Industries, Ltd., and Unica Catalyst MC-109, Riken Fixer RC series, Riken Fixer MX series, and Riken Fixer RZ- manufactured by Miki Riken Kogyo Co., Ltd. 5 and the like can be mentioned.

As the compound having one or more isocyanate groups or blocked isocyanate groups, monofunctional (mono) isocyanate compounds such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate and naphthalene isocyanate, and polyfunctional isocyanate compounds can be used.

The polyisocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule, and a known polyisocyanate compound can be used. Examples of the polyfunctional isocyanate compound include diisocyanate compounds such as alkylene diisocyanate, aryl diisocyanate and cycloalkyl diisocyanate, triisocyanate compounds, and modified polyisocyanate compounds such as dimers or trimers of the diisocyanate compounds. The alkylene diisocyanate preferably has 1 to 12 carbon atoms.

Examples of the diisocyanate compound include 2,4 or 2,6-tolylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylenediisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and decamethylene diisocyanate. Dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, phenylenediisocyanate, tolylen or naphthylene diisocyanate, 4,4'-methylene-bis (phenylisocyanate), 2,4'-methylene-bis (Phenylisocyanate), 3,4'-methylene-bis (phenylisocyanate), 4,4'-ethylene-bis (phenylisocyanate), ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'- Diisocyanate-1,4-dimethylcyclohexane, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,3-dimethylcyclohexane, 1-methyl-2,4-diisocyanatecyclohexane, 4, 4'-methylene-bis (cyclohexamethylene), 3-isocyanate-methyl-3,5,5-trimethylcyclohexylisocyanate, acid-diisocyanate dimerate, ω, ω'-diisocyanate diethylbenzene, ω, ω'-diisocyanate dimethyltoluene , Ω, ω'-diisocyanate diethyltoluene, bis (2-isocyanate ethyl) fumarate ester, 1,4-bis (2-isocyanate-prop-2-yl) benzene, and 1,3-bis (2-isocyanate) -Prop-2-yl) benzene can be mentioned.

Examples of the triisocyanate compound include triphenylmethane triisocyanate, dimethyltriphenylmethanetetraisocyanate, and tris (isocyanatophenyl) -thiophosphate.

The modified polyisocyanate compound derived from the diisocyanate compound is not particularly limited as long as it has two or more isocyanate groups, and is, for example, a biuret structure, an isocyanurate structure, a urethane structure, a uretdione structure, an allophanate structure, and three. Examples thereof include polyisocyanates having a body structure and the like, and adducts of aliphatic isocyanates of trimerolpropane. Polymeric MDI (MDI = diphenylmethane diisocyanate) can also be used as a polyfunctional isocyanate compound.

The polyfunctional isocyanate compound may be used alone or in combination of two or more.

The isocyanate group contained in the polyfunctional isocyanate compound may be a blocked isocyanate group as it is or may be a blocked isocyanate group blocked by a blocking agent. Blocking agents include pyrazoles such as 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4-bromopyrazole, pyrazole; phenol, methylphenol, Phenols such as chlorphenol, iso-butylphenol, tert-butylphenol, iso-amylphenol, octylphenol, nonylphenol; lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam; , Acetylacetone, methyl acetoacetate, ethyl acetoacetate and other active methylene compounds; formaldehyde, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime and other oximes; imidazole, 2-methylimidazole Oxime compounds such as; sodium bisulfite and the like. Among these, pyrazoles and oximes are preferable from the viewpoint of water repellency.

As the polyfunctional isocyanate compound, a water-dispersible isocyanate obtained by imparting water dispersibility to the polyisocyanate by introducing a hydrophilic group into the polyisocyanate structure to have a surface-active effect can also be used. Further, in order to promote the reaction, a known catalyst such as organic tin or organic zinc can be used in combination.

The above-mentioned cross-linking agent or catalyst may be used alone or in combination of two or more.

(fiber)
The fiber may be either a natural fiber or a chemical fiber. Examples of natural fibers include plant fibers such as cotton, cannabis, flax, palm and rush; animal fibers such as wool, goat hair, mohair, cashmere, camel and silk; and mineral fibers such as asbestos. Examples of chemical fibers include inorganic fibers such as rock fiber, metal fiber, graphite, silica, and titanate; regenerated cellulose fibers such as rayon, cupra, biscous, polynosic, and purified cellulose fibers; melt-spun cellulose fibers; milk. Protein-based fibers such as protein and soybean protein; Regenerated / semi-synthetic fibers such as regenerated silk and alginate fiber; Polyamide fiber, polyester fiber, cationic dyeable polyester fiber, polyvinyl fiber, polyacrylic alcohol fiber, polyurethane fiber, acrylic fiber, polyethylene Examples thereof include synthetic fibers such as fibers, polyvinylidene fibers, and polystyrene fibers. Further, two or more kinds of these fibers may be composited (blended, mixed fiber, mixed weaving, mixed knitting, etc.).

Examples of the polyester fiber include polyethylene terephthalate (PET) fiber, polylactic acid (PLA) fiber, polytrimethylene terephthalate (PTT) fiber, polybutylene terephthalate (PBT) fiber, polypropylene terephthalate (PPT) fiber, and polyethylene naphthalate. (PEN) Fiber, polyarylate fiber, etc. means a fiber composed of a polymer condensed by a reaction for forming an ester bond. Examples of the fiber composited with the polyester fiber include synthetic fibers such as cellulose fiber, polyamide fiber and polyurethane fiber, and natural fiber.

The above-mentioned polyamide fiber means a fiber which requires polyamide and may be composited, for example, nylon 6, nylon 66, nylon 610, nylon 11, nylon 4, nylon 7, aromatic nylon (aramid) and the like. Nylon fiber can be mentioned. Polyamides are usually obtained by condensation by a reaction that forms an amide bond.

Examples of the form of the fiber include a fiber, a woven fabric, a knitted fabric, a cloth, a thread, a cheese, a skein, a cloth in the form of clothing, a carpet, a non-woven fabric, and the like.

The water repellent composition of the present invention is preferably used for cotton, nylon fibers, polyester fibers or composite fibers of two or more of these.

(Fiber treatment)
Examples of the method for treating the fiber with the treatment liquid include a processing method such as dipping, spraying, and coating, a processing method by a cleaning method, and the like. When the water-repellent composition contains water, it is preferable to attach the water-repellent composition to the fibers and then dry the treated fibers to remove water.

In the water-repellent fiber product, the amount of the water-repellent composition adhering to the fiber can be appropriately adjusted according to the required degree of water repellency and durable water repellency, but is converted into solid content with respect to the fiber. Therefore, the amount of the water repellent composition adhered ^{is preferably adjusted to 0.01 to 10 g / m 2,} and more preferably 0.05 to 5 g / m ² .

After treating the fibers with the above treatment liquid, it is preferable to appropriately heat-treat the fibers. The temperature condition is not particularly limited, but is usually about 110 to 180 ° C.

In the water-repellent fiber product, in particular, when it is desired to improve the durable water repellency, the above-mentioned step of treating the fiber with the above-mentioned treatment liquid (hereinafter referred to as the water-repellent treatment step) and the above-mentioned cross-linking agent are attached to the fiber. It is preferable to make the fibers water-repellent by a method including a step of heating the fibers (hereinafter referred to as a cross-linking step).

In the cross-linking step, for example, the object to be treated (fibers after the water-repellent treatment step) is immersed in a liquid obtained by dissolving the cross-linking agent in an organic solvent or emulsified and dispersed in water, and the object to be treated after immersion is dried. A method of advancing the reaction between the cross-linking agent and the fiber and the water-repellent composition by attaching the cross-linking agent and then heating is mentioned. In order to sufficiently proceed the reaction of the cross-linking agent and more effectively improve the durable water repellency, the heating at this time is preferably performed at 110 to 180 ° C. for 1 to 5 minutes.

In addition, excessive use of the above-mentioned cross-linking agent may impair the texture. The cross-linking agent is preferably used in an amount of 0.1 to 50% by mass, particularly preferably 0.1 to 10% by mass, based on the object to be treated (fiber).

Since the water-repellent fiber product does not use a fluorine-based compound, it can be made environmentally friendly. The above water-repellent textile products have excellent water repellency, durable water repellency, and exhibit a flexible texture. Therefore, down side fabrics, coats, blousons, windbreakers, blouses, dress shirts, skirts, slacks, gloves, etc. It is suitably used for textile applications such as hats, duvet side areas, duvet drying covers, curtains, tents or umbrellas, clothing applications, non-clothing applications, etc.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The terms "part" and "%" in the example represent "parts by mass" and "% by mass", respectively.

<Synthesis of resin (A)>
Manufacturing example 1
601.2 parts of a mixture of stearic acid and palmitic acid (stearic acid / palmitic acid = 65/35 (mass ratio)) was charged into a reaction vessel equipped with a stirrer, a dehydration tube, a cooling tube, a thermometer and a nitrogen gas introduction tube. After heating and melting, 207.2 parts of tetraethylenepentamine was added. After raising the temperature to 180 ° C. in a nitrogen atmosphere, the temperature is maintained at 180 ° C. to 200 ° C. for 3 hours while removing the water generated by the reaction from the system, and heating is performed when the reaction-generated water reaches 39.4 parts by mass. It was stopped and cooled to obtain an amide resin (1). Subsequently, 188.5 parts of decanoic acid was added to the amide resin (1), and the reaction was carried out at 180 ° C. to 200 ° C. for 3 hours while removing the water generated by the reaction from the system again to obtain the amide resin (2). It was. After cooling this amide resin (2) to 80 ° C., 15 to 30 parts of isopropyl alcohol was added to 100 parts of the resin content, and 1002 parts of ion-exchanged water heated to 80 ° C. and a nonionic surfactant (trade name). 18.8 parts of "Epan 720" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was added and stirred. 202.5 parts of epichlorohydrin as a cationizing agent was added to the suspended reaction solution, and the suspension was kept warm at 80 ° C. to 85 ° C. for about 2 to 4 hours, and then cooled to room temperature. , An aqueous dispersion of resin (A1) was obtained.

[Preparation of water repellent composition]
Example 1
60 parts (in terms of solid content) of the aqueous dispersion of the resin (A1) obtained in Production Example 1 as the component (A) and an emulsion of a long-chain alkyl group-containing silicone as the component (B) (trade name "X-52"). -8046 "Shin-Etsu Chemical Co., Ltd. (solid content concentration 40%) was mixed in 40 parts (solid content conversion) to prepare a water repellent composition having a solid content concentration of 15%.

Examples 2-8 and Comparative Examples 1-8
It was produced in the same procedure as in Example 1 except that the composition was changed to that in Table 1.

[Manufacturing of water-repellent fiber products]
A polyester woven fabric (manufactured by Polyester Tropical Teijin Limited) is immersed in a treatment liquid (solid content concentration 1%) obtained by diluting the water repellent composition obtained in Example 1 with water, and then the water repellent composition is obtained. The polyester woven fabric to which the material was attached was dried in a circulating air dryer at 180 ° C. for 5 minutes to obtain a water-repellent fiber product. The amount of the water-repellent composition adhered to the polyester woven fabric was 1.3 g / m ² . Water-repellent fiber products were produced in the same manner for each of the water-repellent composition of Examples 2 to 8 and Comparative Examples 1 to 8.

The water-repellent fiber products obtained above were evaluated as follows.

(Evaluation of water repellency of textile products)
The test was conducted with the shower water temperature set to 20 ° C. according to the spray method of JIS L 1092 (2009). The results were visually evaluated according to the following grades.
Water repellency: Condition 5: No wetness adhered to the surface 4: Slightly adhered to the surface Wetness 3: Partial wetness on the surface 2: Wetness on the surface 1: Wetness on the entire surface Item 0: Both front and back sides are completely moist.

(Evaluation of durable water repellency of textile products)
The water-repellent fiber product was washed 10 times (HL-10) by the 103 method of JIS L 0217 (1995), and the water repellency after air drying was evaluated in the same manner as the water repellency evaluation method.

(Evaluation of texture of textile products)
The water-repellent fiber product was evaluated by the tactile sensation of the hand according to the criteria shown below.
×: Hard △: Slightly hard ○: Soft ◎: Very soft

表１の各成分の質量部は固形分換算の値であり、表中の注釈及び略語は、以下の通りである。
※（Ａ）成分と（Ｂ）成分との質量比率（固形分換算）

（化合物の略語及び詳細）
Ｘ−５２−８０４６：長鎖アルキル基含有シリコーンのエマルジョン 信越化学工業（株）製 固形分濃度４０％
Ｘ−５１−１３０２Ｍ：ＭＱレジンのエマルジョン 信越化学工業（株）製 固形分濃度１７％

The mass part of each component in Table 1 is a value in terms of solid content, and the annotations and abbreviations in the table are as follows.
* Mass ratio of component (A) and component (B) (in terms of solid content)

(Abbreviations and details of compounds)
X-52-8046: Emulsion of silicone containing long-chain alkyl group Shin-Etsu Chemical Co., Ltd. Solid content concentration 40%
X-51-1302M: MQ resin emulsion Shin-Etsu Chemical Co., Ltd. Solid content concentration 17%

Claims (8)

Polyamine (a1) having a secondary amino group, resin (A) which is a reaction product of monocarboxylic acid (a2) having 10 to 36 carbon atoms and epihalohydrin (a3-1) or glycidol (a3-2), and silicone. Including (B)
A water repellent composition having a mass ratio ((A) / (B)) of the resin (A) and the silicone (B) of more than 1 and less than 99 in terms of solid content. The component (a1) is the general formula (1): H ₂ N-[(CH ₂ ) _m NH] _n- H (in the formula, m represents an integer of 1 to 6 and n represents an integer of 2 to 6). The water repellent composition according to claim 1, which is a compound represented by. The water repellent composition according to claim 1 or 2, wherein the component (a2) is an aliphatic monocarboxylic acid having 16 to 24 carbon atoms. The water repellent composition according to any one of claims 1 to 3, wherein the component (a3-1) is epichlorohydrin. The water repellent composition according to any one of claims 1 to 4, wherein the component (B) is a long-chain alkyl group-containing silicone and / or a silicone resin. The water repellent composition according to any one of claims 1 to 5, wherein the above (A) / (B) are 3 to 9 in terms of solid content. A water-repellent fiber product comprising the fiber and the water-repellent composition according to any one of claims 1 to 6 attached to the fiber. A method for producing a water-repellent fiber product, which comprises a step of treating the fiber with a treatment liquid containing the water-repellent composition according to any one of claims 1 to 6.