TW202118852A - Water-repellent composition, water-repellent fiber product, and manufacturing method of water-repellent fiber product wherein the water repellent composition contains resin (A) and silicone (B) - Google Patents

Abstract

The present invention provides a non-fluorine-based water repellent composition, which can provide fiber products with an excellent and durable water repellency and a good texture. A water repellent composition contains resin (A) and silicone (B). The resin (A) is a reactant of polyamine (a1) with a secondary amino group, monocarboxylic acid (a2) with carbon numbers of 10 to 36, and epihalohydrin (a3-1) or glycidol (a3-2). The mass ratio ((A)/(B)) of the resin (A) and the silicone (B) is greater than 1 and less than 99 in terms of solid content.

Description

Water-repellent composition, water-repellent fiber product, and manufacturing method of water-repellent fiber product

The invention relates to a water-repellent composition, a water-repellent fiber product, and a manufacturing method of the water-repellent fiber product.

Conventionally, as a water-repellent agent used in fibers, a fluorine-based water-repellent is known, and it is known that a fiber product is treated with the fluorine-based water-repellent to impart water-repellency to the surface thereof. Such a fluorine-based water repellent is generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group.

However, although fiber products treated with fluorine-based water repellents exhibit excellent water repellency, monomers with fluoroalkyl groups are expensive, so they are not economically satisfactory, and monomers with fluoroalkyl groups are difficult Decomposability, so there are problems in 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 obtained by emulsifying and dispersing a specific non-fluorine-based polymer, and Patent Document 2 proposes a silicone water repellent containing polyorganosiloxane and metal alkoxide Composition.

【Prior Technical Literature】

【Patent Literature】

[Patent Document 1] JP 2006-328624 A

[Patent Document 2] Japanese Patent Application Publication No. 7-305053

However, in terms of practicality, the water repellency of the fiber product treated with a non-fluorine-based water repellent described in Patent Document 1 is still insufficient, and the water repellency (durable water repellency) of the fiber product after washing is also not satisfactory. satisfaction. In addition, the silicone-based water-repellent agent of Patent Document 2 has the following problem: most of the fiber products treated with it have insufficient texture.

The subject of the present invention is to provide a non-fluorine-based water repellent composition capable of providing fiber products with excellent water repellency and durable water repellency and good texture.

The inventors of the present invention conducted intensive studies to solve the above-mentioned problems. As a result, they found that the above-mentioned problems can be solved by a water-repellent composition containing a specific resin and silicone in a specific mass ratio, thereby completing the present invention. The specified reactant of polyamine, monocarboxylic acid and epihalohydrin or glycidol. That is, the present invention relates to the following water repellent composition.

1. A water-repellent composition characterized by containing resin (A) and silicone (B), and the resin (A) is a polyamine (a1) with a secondary amino group, and a monocarboxylate with a carbon number of 10 to 36 The reactant of acid (a2) and epihalohydrin (a3-1) or glycidol (a3-2);

The mass ratio ((A)/(B)) of the resin (A) and the silicone (B) is greater than 1 and less than 99 in terms of solid content.

2. The water-repellent composition as described in the above item 1, wherein the component (a1) has the general formula (1): H ₂ N-[(CH ₂ ) _m NH] _n -H (where m represents 1 ~6 is an integer, n represents an integer from 2 to 6).

3. The water repellent composition as described in the above item 1 or 2, wherein the component (a2) is an aliphatic monocarboxylic acid having 16 to 24 carbon atoms.

4. The water repellent composition as described in any one of the above items 1 to 3, wherein the component (a3-1) is epichlorohydrin.

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

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

7. A water-repellent fiber product characterized by comprising fiber and the water-repellent composition described in any one of the above items 1 to 6 attached to the fiber.

8. A method for producing a water-repellent fiber product, characterized by comprising a step of treating fibers with a treatment liquid containing the water-repellent composition described in any one of items 1 to 6 above.

The water-repellent composition of the present invention, compared with the conventional non-fluorine-based water-repellent, can impart superior water repellency and durable water repellency to fiber products, and the fiber product also has a good texture.

〔Water repellent composition〕

The present invention relates to a water-repellent composition containing resin (A) (hereinafter referred to as (A) component.) and silicone (B) (hereinafter referred to as (B) component), and the resin (A) Secondary amine Polyamine (a1) (hereinafter referred to as component (a1).), monocarboxylic acid (a2) with 10 to 36 carbon atoms (hereinafter referred to as component (a2).) and epihalohydrin (a3-1) ( Hereinafter referred to as (a3-1) component.) or a reactant of glycidol (a3-2) (hereinafter referred to as (a3-2) component.); the mass ratio of (A) component to (B) component ((A) )/(B)) is greater than 1 and less than 99 in terms of solid content.

<Resin (A)>

(a1) The component is not particularly limited as long as it is a polyamine having a secondary amino group, and various conventional polyamines can be used. (a1) The component may have a primary amino group or a tertiary amino group in its molecule. (a1) A component can be used individually by 1 type or in combination of 2 or more types.

(a1) The component includes, for example, the general formula (1): H ₂ N-[(CH ₂ ) _m NH] _n -H (where m represents an integer from 1 to 6, and n represents an integer from 2 to 6.) Show the compound and so on. The component (a1) desirably uses the compound represented by the general formula (1).

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

Examples of the above-mentioned polyethylene polyamine include diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and the like. Examples of the above-mentioned polypropylene polyamine include dipropylene triamine, tripropylene tetramine, tetrapropylene pentamine, pentapropylene hexaamine, and the like.

(a1) Among the ingredients, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are easy to obtain as general industrial reagents. They are low-viscosity liquids at room temperature and are easy to handle, and are supplied from stable It is also ideal in terms of the aspect.

(a2) The component is not particularly limited as long as it is a monocarboxylic acid having a carbon number of 10 to 36, and various conventional monocarboxylic acids can be used. (a2) A component can be used individually by 1 type or in combination of 2 or more types.

(a2) The component includes, for example, an aromatic monocarboxylic acid having 10 to 36 carbon atoms, an aliphatic monocarboxylic acid having 10 to 36 carbon atoms, and the like.

As the above-mentioned aromatic monocarboxylic acid having 10 to 36 carbon atoms, for example, methyl Benzoic acid, naphthoic acid, etc. In addition, the aromatic monocarboxylic acid may have a substituent such as an alkyl group or alkenyl group having 1 to 12 carbon atoms.

As the above-mentioned aliphatic monocarboxylic acid having 10 to 36 carbon atoms, for example, saturated fatty acids having 10 to 36 carbon atoms, unsaturated fatty acids having 10 to 36 carbon atoms, and derived from 10 to 36 carbon atoms Fatty acids of vegetable fats or animal fats and their acid anhydrides. In addition, in order to facilitate the reaction, the aliphatic monocarboxylic acid having a carbon number of 10 to 36 may also be a halide such as chlorine.

The above-mentioned saturated fatty acids include, for example, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, ceric acid, octadecanoic acid, beeswaic acid, etc. .

Examples of the above-mentioned unsaturated fatty acids include palmitoleic acid, oleic acid, erucic acid, linoleic acid, hypolinoleic acid, codoleic acid, and arachidonic acid.

Examples of the fatty acids derived from vegetable fats or animal fats include castor oil fatty acid, coconut oil fatty acid, palm oil fatty acid, tallow fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, and pine oil fatty acid.

From the viewpoints of excellent water repellency and durable water repellency of the fiber product and excellent reactivity to the component (a1), the component (a2) is preferably an aliphatic monocarboxylic acid having 10 to 36 carbon atoms. In addition, from the same viewpoint, the component (a2) is more preferably an aliphatic monocarboxylic acid having 16 to 24 carbon atoms.

(a3-1) The component is not particularly limited as long as it is an epihalohydrin, and various conventional epihalohydrins can be used. (a3-1) A component can be used individually by 1 type or in combination of 2 or more types.

(a3-1) As a component, epichlorohydrin, epibromohydrin, epiiodohydrin, methyl epichlorohydrin, etc. are mentioned, for example. From the viewpoint of low price and easy handling, the component (a3-1) is desirably epichlorohydrin.

(a3-2) The component is not particularly limited as long as it is glycidol, and various conventional glycidols can be used. (a3-2) A component can be used individually by 1 type or in combination of 2 or more types.

(a3-2) Ingredients, for example 2,3-epoxy-1-propanol, 3,4-epoxy-1-butanol Alcohol etc.

<Physical properties and manufacturing method of resin (A)>

(A) The usage amount of the (a1) component, (a2) component, and (a3-1) component or (a3-2) component in the component is not specifically limited.

(A) The usage amount of (a1) component and (a2) component in component, if the number of primary amine groups contained in component (a1) is set to M, the number of secondary amine groups is set to N , Relative to (a1) component 1 mol, (a2) component is ideally about (M) to (M+0.9N) mol. When the usage amount of (a2) component is (M) mol or more, there is a tendency that the water repellency and durable water repellency of fiber products are more excellent; the usage amount of (a2) component is (M+0.9N) mo In the case of less than ears, the stability of the (A) component becomes more excellent. In addition, when the component (a1) is a mixture in which a plurality of polyamines are mixed, M needs to be an average value.

From the viewpoint of emulsification and storage stability of (A) component, the usage amount of (a3-1) component or (a3-2) component in (A) component is 1 mol relative to (a1) component, It is desirably about 0.1N to 1.5N moles, and more desirably about 0.3N to 0.75N moles. In addition, N is the same as described above.

(A) The manufacturing method of component is not particularly limited as long as it is a method of reacting component (a1), component (a2) and component (a3-1) or component (a3-2), and various conventional manufacturing methods can be exemplified . Specifically, for example, the following method is mentioned: (a1) component and (a2) component are heated to 150°C or higher, and the by-product water is removed while reacting for about 2 to 8 hours, and then dissolving Or disperse it in a solvent or water, then add (a3-1) component or (a3-2) component, and make it react for about 2-6 hours. In the above reaction, when it is difficult to disperse the reactant composed of the component (a1) and the component (a2), heating may be performed in the range of 40°C or higher and 120°C or lower, or an emulsifying and dispersing agent may be used in combination.

(A) The form of the component is not particularly limited. (A) Ingredients can be used directly, It can also be used as a solution or dispersion prepared by dissolving or dispersing (including suspension and emulsification) in a solvent or water. (A) The component is desirably an aqueous dispersion.

(A) The preparation method of the said aqueous dispersion liquid of a component is not specifically limited, Various conventional methods can be utilized. Specifically, for example, a method of dispersing component (A) in water in the presence or absence of an emulsifier; in the above-mentioned production method, a dispersion liquid of component (A) obtained in the presence of water is used as it is The method; or the method of using the commercially available product of the aqueous dispersion of component (A), etc.

The above-mentioned dispersion method is not particularly limited. The dispersion method includes, for example, a mechanical emulsification method for forced emulsification of component (A) and water; inversion emulsification in which water is slowly added to the melt of component (A) to reverse the oil phase and water. Method; high-pressure emulsification method in which (A) component and water are emulsified under high pressure. The emulsifier used in the mechanical emulsification method is not particularly limited, and examples thereof include a homomixer, a high-pressure homogenizer (manufactured by Manton Gaulin), and a ball mill.

The emulsifier is not particularly limited, and various conventional emulsifiers can be used. Examples of emulsifiers include cationic surfactants, nonionic surfactants, and reactive emulsifiers. In addition, the amount of the emulsifier used is generally in the range of about 1 to 10% by mass in terms of solid content relative to the component (A).

Examples of the cationic surfactant include tetraalkylammonium chloride, trialkylbenzylammonium chloride, alkylamine acetate, alkylamine hydrochloride, oxyethylene alkylamine, Polyoxyethylene alkylamine, alkylamine acetate, cationized starch, etc. The above-mentioned cationized starch includes, for example, a group of raw starches such as corn, potato, tapioca, wheat, and rice, which are selected from primary, secondary, tertiary, and quaternary amine groups. Cationized starch made from at least one of the basic nitrogen bases.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, and sorbitan higher fatty acids Esters, polyoxyethylene sorbitan higher fatty acid esters, polyoxyethylene higher fatty acid esters, glycerol higher fatty acid esters, polyalkylene oxide block copolymers, etc., specifically, polyoxyethylene Lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene styryl phenyl ether, sorbitan monolaurate, sorbitan trioleate, polyoxyethylene Ethylene sorbitan monolaurate, polyoxyethylene monolaurate, polyoxyethylene monooleate, oleic acid monoglyceride, stearic acid monoglyceride, polyoxyethylene‧polyoxypropylene‧block copolymer Things and so on.

The reactive emulsifier is not particularly limited as long as it has a functional group containing a double bond capable of radical polymerization, and various conventional emulsifiers can be used. Examples of double bonds that can be radically polymerized include (meth)acryloyl groups and allyl groups.

Examples of the reactive emulsifier include polyoxyethylene alkyl ethers having at least one functional group containing a double bond capable of radical polymerization in the molecule, and polyoxyethylene alkyl ethers having at least one functional group in the molecule. Sulfosuccinate salt of vinyl alkyl ether, sulfate ester salt of polyoxyethylene alkyl ether having at least one functional group in the molecule, polyoxyethylene phenyl having at least one functional group in the molecule Ether, sulfosuccinate salt of polyoxyethylene phenyl ether having at least one functional group in the molecule, sulfate ester salt of polyoxyethylene phenyl ether having at least one functional group in the molecule, Polyoxyethylene alkyl phenyl ether having at least one functional group in the molecule, sulfosuccinate salt of polyoxyethylene alkyl phenyl ether having at least one functional group in the molecule, having Sulfate salt of polyoxyethylene alkyl phenyl ether having at least one functional group, polyoxyethylene aralkyl phenyl ether having at least one functional group in the molecule, having at least one functional group in the molecule The sulfosuccinate salt of the polyoxyethylene aralkylphenyl ether of the base, the sulfate ester salt of the polyoxyethylene aralkylphenyl ether having at least one functional group in the molecule, and the sulfate ester salt of the polyoxyethylene aralkylphenyl ether having at least one in the molecule Phosphate ester salt of polyoxyethylene alkylphenyl ether with one functional group, aliphatic or aromatic carboxylate, acidic polyoxyethylene alkylphenyl ether with at least one functional group in the molecule Phosphoric acid (meth)acrylate emulsifier, rosin glycidyl acrylate modified anhydride (refer to Japan Various emulsifiers such as emulsifiers described in Japanese Patent Application Laid-Open No. 4-256429), Japanese Patent Application Publication No. 63-23725, Japanese Patent Application Publication No. 63-240931, and Japanese Patent Application Publication No. 62-104802.

In addition, reactive emulsifiers obtained by replacing polyoxyethylene in the above-mentioned reactive emulsifier with polyoxypropylene or block copolymerization or random copolymerization of polyoxyethylene and polyoxypropylene can also be cited. Moreover, as these commercially available products, for example, KAYAMER PM-1, KAYAMER PM-2, KAYAMER PM-21 (the above are manufactured by Nippon Kayaku Co., Ltd.); SE-10N, NE-10, NE- 20. NE-30, ADEKA REASOAP SR-10, ADEKA REASOAP SR-20, ADEKA REASOAP ER-20 (the above are manufactured by ADEKA Co., Ltd.); 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 (the above are manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.); ELEMINOL JS-2 (manufactured by Sanyo Chemical Co., Ltd.) ; Latemul K-180 (manufactured by Kao Co., Ltd.) as a representative example.

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

In addition, a protective colloid can also be used as needed. The protective colloid is not particularly limited, and conventional protective colloids can be used. Specifically, for example, colloids obtained by polymerizing anionic monomers, cationic monomers, and other monomers can be cited. Anionic monomers refer to monomers having at least one anionic functional group and one vinyl group. Specifically, examples include monocarboxylic acids such as (meth)acrylic acid and crotonic acid; maleic acid, Fumaric acid, itaconic acid, muconic acid, citraconic acid and other dicarboxylic acids; vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, (meth)ene Organic sulfonic acids such as propyl sulfonic acid; or the sodium and potassium salts of various organic acids. Cationic monomer refers to a monomer having at least one cationic functional group and one vinyl group, specifically, Examples include allylamine; and N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl ( Vinyl monomers with tertiary amino groups such as meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, etc., or inorganic or organic acids such as hydrochloric acid, sulfuric acid, acetic acid, etc. Acid salts; or quaternary ammonium salts obtained by reacting the vinyl monomers containing tertiary amine groups with quaternary agents such as methyl chloride, benzyl chloride, dimethyl sulfate, epichlorohydrin, etc. The vinyl monomer and so on. Examples of monomers other than anionic monomers and cationic monomers include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N,N-diethyl (Meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N- Isopropyl (meth)acrylamide, N-tertiary butyl (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, etc. Alkyl acrylates; allyl-containing allyl-based monomers such as allyl alcohol; N-substituted acrylamide-based monomers such as isopropylacrylamide; (meth)acrylonitrile, etc. ; And as a two-functional vinyl single-system methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide and other bisacrylamide monomers and ethylene glycol two ( Diacrylate monomers such as meth)acrylate, diethylene glycol di(meth)acrylate, diallylamine, divinylbenzene, etc.; as a multifunctional ethylene with 3 or more vinyl groups The base monomers include 1,3,5-triacryloyl hexahydros-triazine, triallyl isocyanurate, triallylamine, tetramethylolmethane tetraacrylate, etc. In addition, these polymerization methods may be any conventional methods such as radical polymerization methods.

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

(A) The physical properties of the aqueous dispersion of the component are not particularly limited. (A) The concentration of the above-mentioned aqueous dispersion of the component, considering workability, etc., ideally has a solid content of about 0.1-50% by weight. In addition, considering the dispersibility of the above-mentioned aqueous dispersion of the component (A), the ideal system has a volume average particle size of about 0.2 to 10 μm. Furthermore, the pH of the above-mentioned aqueous dispersion of component (A) is ideally 3~7 About, and its appearance is usually white to yellowish white.

For component (A), set the number of secondary amino groups present in component (a1) as x, and combine the secondary amino group of component (a1) with component (a3-1) or (a3- 2) When the number of tertiary amino groups generated by the reaction of the components is set to y, the value of y/x is more preferably 0.1 to 0.95. By setting the value of y/x in this range, the water repellency and durable water repellency of the fiber product are more excellent. For the component (A), the value of y/x is preferably about 0.2 to 0.9, particularly preferably 0.2 to 0.7 from the viewpoint of excellent water repellency and durable water repellency of the fiber product.

<Silicone (B)>

(B) The component is not particularly limited, and various conventional silicones can be used. (B) A component can be used individually by 1 type or in combination of 2 or more types.

(B) The component includes, for example, silicone resin and silicone oil.

(Silicone resin)

The aforementioned silicone resin is not particularly limited. Examples of the aforementioned silicone resin include: T unit and/or Q unit as constituent components and at least one type of silicone unit selected from M unit and D unit as other than the T unit and/or Q unit An organopolysiloxane with a three-dimensional structure as a constituent unit. In addition, M unit, D unit, T unit, and Q unit respectively mean (R) ₃ SiO _1/2 unit, (R) ₂ SiO _2/2 unit, RSiO _3/2 unit, and SiO _4/2 unit.

The R in the above-mentioned M unit, D unit, T unit and Q unit can be exemplified independently of each other: substituted or unsubstituted monovalent hydrocarbon groups with 1 to 12 carbons, hydroxyl groups, hydrolyzable groups with 1 to 6 carbons, and the like.

Examples of the above-mentioned monovalent hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, 2- Ethylhexyl, nonyl, decyl, dodecyl, etc. alkyl; cyclopentyl, cyclohexyl, etc. cycloalkyl; vinyl, allyl, propenyl, isopropenyl, butenyl, pentene Alkenyl, hexenyl, cyclohexenyl, etc.; benzene Aryl groups such as benzyl, tolyl, xylyl, α-naphthyl, β-naphthyl, etc.; aralkyl groups such as benzyl, 2-phenethyl, 3-phenylpropyl, etc.; or hydrogen of these groups Groups in which part or all of the atoms are substituted by halogen atoms such as F, Cl, Br, or cyano groups (for example, 3-chloropropyl, 3,3,3-trifluoropropyl, 2-cyanoethyl, etc.).

Examples of the above-mentioned hydrolyzable group include alkoxy groups such as methoxy and ethoxy groups.

The silicone resin may include, for example, MQ resin containing the M unit and the Q unit as the main components; TD resin containing the T unit and the D unit as the main components; and the M unit and T unit as the main components. MT resin; MDQ resin composed of the M unit, D unit and Q unit; MDT resin composed of the M unit, D unit and T unit; and composed of the M unit, D unit, T unit, and Q unit MDTQ resin and so on.

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

(Silicone oil)

The aforementioned silicone oil is not particularly limited. Examples of the above-mentioned silicone oil include linear organopolysiloxanes. Examples of the organopolysiloxane include those having an organic group in at least any one of the side chain and the terminal.

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

The above-mentioned ordinary silicones include, for example, dimethyl silicone, methyl phenyl silicone, methyl hydrosilicone, and the like.

The above-mentioned modified silicones include, for example, silicones containing amino groups, silicones containing epoxy groups, silicones containing methanol groups, silicones containing mercapto groups, silicones containing carboxyl groups, and polyethers containing Silicone, silicone containing long-chain alkyl, silicone containing aralkyl, silicone containing long-chain alkyl‧aralkyl, silicone containing higher fatty acid ester group, silicone containing higher aliphatic Amino-based silicones, etc.

The above-mentioned amino group-containing silicones can be exemplified by compounds having an organic group containing an amino group and/or an imine group in at least any one of the side chain and the end of the silicone structure. Commercial products of silicone containing amino groups include, for example: WACKER FINISH WR301, WR1100, WR1200, WR1300, WR1600 (the above are manufactured by Asahi Kasei WACKER SILICONE); KF8005, KF-868, KF-864, KF-393, KF-8021 (the above are made by Shin-Etsu Chemical Co., Ltd.); TSF-4709, XF42-B1989 (the above are MOMENTIVE PERFORMANCE MATERIALS, made by Japan Co., Ltd.); BY16-872, SF-8417, BY16-853U, BY16- 892 (The above are manufactured by Toray Dow Corning Co., Ltd.), etc.

The above-mentioned epoxy-containing silicones can be exemplified by compounds having an epoxy-containing organic group in at least any one of the side chain and the end of the silicone structure. Commercial products of epoxy-containing silicones 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 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

The above-mentioned silicone containing a methanol group can be exemplified by compounds having an organic group containing a methanol group in at least any one of the side chain and the end of the silicone structure. Commercial products of silicone containing methanol groups, for example: X-22-4039, X-22-4015, X-22-170BX, X-22-170DX, KF-6000, KF-6001, KF-6002 , KF-6003 (the above is made by Shin-Etsu Chemical Co., Ltd.), etc.

The above-mentioned silicone containing mercapto groups can be exemplified by compounds having organic groups containing mercapto groups in at least any position of the side chain and the end of the silicone structure. Commercial products of sulfhydryl-containing silicones include, for example, KF-2001, KF-2004, X-22-167B, X-22-167C (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The above-mentioned silicone containing carboxyl group can be exemplified by compounds having an organic group containing a carboxyl group in at least any one of the side chain and the terminal of the silicone structure. Commercial products of carboxyl group-containing silicones include, for example, X-22-3701E, X-22-162C (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The polyether group-containing silicone can be exemplified by compounds having an organic group containing a polyether group in at least any one of the side chain and the end of the silicone structure. The above-mentioned polyether groups include, for example, polyoxyalkylene groups such as polyoxyethylene groups, polyoxypropylene groups, polyoxyethylene·polyoxypropylene block structures, and the like. Commercial products of silicone containing polyether groups, for example: SF8410 (manufactured by Toray Dow Corning Co., Ltd.); KF-6004, KF-6011, KF-6012, KF-6020, KF-6204, X- 22-4515 (The above is made by Shin-Etsu Chemical Co., Ltd.), etc.

The above-mentioned long-chain alkyl-containing silicones can be exemplified by compounds having organic groups containing long-chain alkyl groups in at least any position of the side chain and the end of the silicone structure. The long-chain alkyl group is not particularly limited, but from the viewpoint of excellent water repellency and durable water repellency of the fiber product, it is preferably an alkyl group having 6 or more carbon atoms, and more preferably an alkyl group having 6 to 36 carbon atoms. Commercial products of silicones containing long-chain alkyl groups include, for example: SF8416 (manufactured by Toray Dow Corning Co., Ltd.); KF-412, KF-413, KF-414, KF-415, KF-4003, KF -4701, KF-4917, KF-7235B, X-22-1877, X-52-8046 (the above are made by Shin-Etsu Chemical Co., Ltd.), etc.

The above-mentioned aralkyl group-containing silicones can be exemplified by compounds having an aralkyl group-containing organic group in at least any one of the side chain and the end of the silicone structure. Examples of the aralkyl group include benzyl, 2-phenethyl, 3-phenylpropyl, and the like. Examples of commercially available products of aralkyl-containing silicones include KF-410 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The above-mentioned long-chain alkyl and aralkyl-containing silicones can be exemplified by compounds having organic groups containing the above-mentioned long-chain alkyl groups and the above-mentioned aralkyl groups in at least any position of the side chain and the end of the silicone structure Wait. Commercially available silicones containing long-chain alkyl and aralkyl groups, for example: SH203 (manufactured by Toray Dow Corning Co., Ltd.); X-22-1877 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

The above-mentioned silicone containing higher fatty acid ester groups can be exemplified by compounds having organic groups containing higher fatty acid ester groups in at least any position of the side chain and the terminal of the silicone structure. Examples of commercially available products of silicones containing higher fatty acid ester groups include X-22-715 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The above-mentioned silicone containing higher aliphatic amide group can be exemplified by a compound having an organic group containing the above-mentioned higher aliphatic amide group in at least any position of the side chain and the terminal of the silicone structure. Examples of commercially available products of silicones containing higher aliphatic amide groups include KF-3935 (manufactured by Shin-Etsu Chemical Co., Ltd.).

From the viewpoint of excellent water repellency and durable water repellency of fiber products, component (B) is ideally silicone resin, long-chain alkyl-containing silicone, aralkyl-containing silicone, and long-chain alkyl ‧ aromatic From the same point of view, alkyl silicones are more ideally MQ resins and silicones containing long-chain alkyl groups.

(B) The form of the component is not particularly limited. (B) The component can be used as it is, or it can be used as a solution or dispersion prepared by dissolving or dispersing (including suspension and emulsification) in a solvent or water. (B) The component is ideally an aqueous dispersion.

The method for producing the aqueous dispersion of the component (B) is not particularly limited, and examples include: a method of dispersing the component (B) in water in the presence or absence of an emulsifier; using the aqueous dispersion of the component (B) The method of the commercially available products, etc. The above-mentioned dispersion method and emulsifier are not particularly limited, and examples thereof include the same dispersion method and emulsifier as the above-mentioned dispersion method and emulsifier.

<Additives>

The above-mentioned water-repellent composition may contain various conventional additives as necessary as long as the effect of the present invention is not impaired. The additives include, for example, water repellents other than the above water repellent composition, Surfactants, defoamers, pH adjusters, antibacterial agents, antifungal agents, coloring agents, antioxidants, deodorants, various organic solvents, chelating agents, antistatic agents, catalysts, crosslinking agents described later, antibacterial and deodorant Agent, flame retardant, softener, anti-wrinkle agent, etc. The above-mentioned additives may be used singly or in combination of two or more kinds.

Examples of the defoaming agent include: fat-based defoaming agents such as castor oil, sesame oil, linseed oil, animal and vegetable oils; fatty acid-based defoaming agents such as stearic acid, oleic acid, and palmitic acid; isostearic acid Fatty acid ester-based defoamers such as amyl ester, distearyl succinate, ethylene glycol distearate, butyl stearate, etc.; polyoxyalkylene monoalcohol, di-tertiary amyl phenoxy ethanol, Alcohol defoamers such as 3-heptanol, 2-ethylhexanol, etc.; di-tertiary pentyl phenoxy ethanol, 3-heptyl cyrus, nonyl cyrus, 3-heptyl carbitol Ether-based defoaming agents such as tributyl phosphate and tris(butoxyethyl) phosphate; amine-based defoaming agents such as dipentylamine; polyalkylene amides, alcohols Amine-based defoamers such as acylate polyamine; sulfate-based defoamers such as sodium lauryl sulfate; mineral oil, etc. A defoamer can be used individually by 1 type or in combination of 2 or more types.

Examples of the above-mentioned pH adjusters 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, and nitric acid. , Phosphoric acid, boric acid and other inorganic acids; sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia, alkanolamine, pyridine, morpholine and other bases. A pH adjuster can be used individually by 1 type or in combination of 2 or more types.

Examples of the above-mentioned organic solvents include: aliphatic alcohols with 1 to 8 carbon atoms such as methanol, ethanol, isopropanol, isobutanol, hexanol, and 2-ethylhexanol; acetone, methyl ethyl ketone, methyl isobutyl Base ketones, diisobutyl ketone, cyclohexanone, diacetone alcohol, etc.; ethyl acetate, methyl acetate, butyl acetate, methyl lactate, ethyl lactate, etc.; diethyl ether, Diisopropyl ether, methyl siloxol, ethyl siloxol, butyl siloxol, dioxane, methyl tertiary butyl ether, butyl carbitol and other ethers; ethylene glycol, Diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and other glycols; B Glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl Glycol ethers such as -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-dimethylformamide, acetaniline and other amides. An organic solvent can be used individually by 1 type or in combination of 2 or more types.

As the antistatic agent, it is preferable to use one that does not easily hinder water repellency. Examples of antistatic agents include cationic surfactants such as higher alcohol sulfate ester salts, sulfated oils, sulfonates, quaternary ammonium salts, and imidazoline quaternary salts; polyethylene glycol type, polyol Non-ionic surfactants such as ester type; amphoteric surfactants of imidazoline type quaternary salt, alanine type, betaine type, etc.; antistatic polymer of high molecular compound type; polyalkylamine, etc. An antistatic agent can be used individually by 1 type or in combination of 2 or more types.

[Physical properties and manufacturing method of water repellent composition]

The physical properties of the water repellent composition are not particularly limited. The concentration of the water repellent composition, considering workability, etc., ideally has a solid content of about 0.1 to 50% by weight. In addition, considering the dispersibility of the above-mentioned water-repellent composition, the ideal system has a volume average particle size of about 0.2 to 10 μm. Further, the pH of the water-repellent composition is preferably about 3-7, and the appearance of the water-repellent composition is usually white to yellow-white.

The mass ratio ((A)/(B)) of the component (A) and the component (B) of the water repellent composition is greater than 1 and less than 99 in terms of solid content. When the above-mentioned mass ratio is 1 or less, the texture of the fiber product becomes insufficient. When the above-mentioned mass ratio is 99 or more, the water repellency and durable water repellency of the fiber product are reduced. From the viewpoint of excellent balance of water repellency, durable water repellency, and texture of the fiber product, the above-mentioned mass ratio is preferably about 3 to 9 in terms of solid content.

The content of the component (A) in the water repellent composition is not particularly limited. From the standpoint of the water repellency, durable water repellency and texture of the fiber product, it is compared to the water repellent 100% by mass of the composition is ideally 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. From the viewpoint of excellent water repellency, durable water-repellent, and texture of the fiber product, relative to 100% by mass of the water-repellent composition The solid content conversion is ideally about 3-40% by mass.

The manufacturing method of the water-repellent composition of the present invention is not particularly limited, and various conventional methods can be used. Specifically, for example, a method of mixing (A) component and (B) component, and if necessary, the above-mentioned additives is mentioned. The mixing order of each component is not particularly limited, and it can be mixed starting from any component. In addition, the mixing method is not particularly limited, and various conventional methods such as stirring can be used.

〔Water repellent fiber products〕

The water-repellent fiber product of the present invention can be obtained by treating fibers with a treatment liquid containing the above-mentioned water-repellent composition.

(Treatment liquid)

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

The aforementioned aqueous medium is desirably, for example, water or a mixed solvent of water and a hydrophilic solvent that can be mixed with water. Examples of hydrophilic solvents include methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, hexylene glycol, glycerin, ethylene glycol butyl ether, diethylene glycol butyl ether, 3-methyl Oxy-3-methyl-1-butanol (Solfit), N-methylpyrrolidone, dimethylformamide, dimethylsulfene, etc.

(Crosslinking agent)

For the purpose of improving the durable water repellency of the water-repellent fiber product, the above-mentioned treatment liquid may further contain a crosslinking agent. Examples of the crosslinking agent include melamine resins, compounds having one or more isocyanate groups or blocked isocyanate groups, and the like.

The above-mentioned melamine resin may be a compound having a melamine skeleton, for example, polymethylol melamine such as trimethylol melamine and hexamethylol melamine; part or all of the methylol groups of polymethylol melamine have Alkoxymethyl melamine of alkoxymethyl group with carbon number 1~6; part or all of the methylol group of polymethylol melamine becomes oxymethyl group with carbon number 2-6 Oxymethyl melamine and so on. These melamine resins may be any one of monomers, dimers or higher polymers, or mixtures thereof may also be used. Further, it is also possible to use a co-condensation of urea and a part of melamine. Examples of such melamine resins include BECKAMINE APM, BECKAMINE M-3, BECKAMINE M-3(60), BECKAMINE MA-S, BECKAMINE J-101, and BECKAMINE J-101LF manufactured by DIC Co., Ltd.; United Chemical Industry (Union Chemical Industry) Unika Resin 380K manufactured by Co., Ltd.; RIKEN RESIN MM series manufactured by Miki Riken Kogyo Co., Ltd., etc.

From the viewpoint of promoting the reaction, the above-mentioned melamine resin preferably uses a catalyst. Such a catalyst is not particularly limited as long as it is a commonly used catalyst. Examples include: borofluoride compounds such as ammonium borofluoride and zinc borofluoride; neutral metal salt catalysts such as magnesium chloride and magnesium sulfate ; Inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, etc. In these catalysts, organic acids such as citric acid, tartaric acid, malic acid, maleic acid, lactic acid, etc. can also be used in combination as a co-catalyst. Examples of such a catalyst include: Catalyst ACX, Qatalyst 376, Catalyst O, Catalyst M, Catalyst G (GT), Catalyst X-110, Catalyst GT-3, and Catalyst NFC-1 manufactured by DIC Co., Ltd.; United Chemicals Unika Catalyst 3-P and Unika Catalyst MC-109 manufactured by Industrial Co., Ltd.; Riken Fixer RC series, Riken Fixer MX series and Riken Fixer RZ-5 manufactured by Miki Riken Industry Co., Ltd.

As the above-mentioned compound having one or more isocyanate groups or blocked isocyanate groups, butyl isocyanate, phenyl isocyanate, toluene isocyanate, naphthyl isocyanate, etc. can be used The monofunctional (mono) isocyanate compound, or the multifunctional isocyanate compound.

The polyfunctional isocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule, and conventional polyisocyanate compounds can be used. Examples of polyfunctional isocyanate compounds include diisocyanate compounds such as alkylene diisocyanate, aryl diisocyanate, and cycloalkyl diisocyanate; triisocyanate compounds; dimers or trimers of the diisocyanate compounds, etc. Modified polyisocyanate compounds, etc. The carbon number of the alkylene diisocyanate is desirably 1-12.

Examples of the diisocyanate compound include 2,4 or 2,6-toluene diisocyanate, ethylene diisocyanate, propylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, Tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, Benzene diisocyanate, toluene diisocyanate or naphthalene diisocyanate, 4,4'-methylene-bis(phenyl isocyanate), 2,4'-methylene-bis(phenyl isocyanate), 3, 4'-methylene-bis(phenyl isocyanate), 4,4'-ethylene-bis(phenyl isocyanate), ω,ω'-diisocyanate-1,3-di Methylbenzene, ω,ω'-diisocyanato-1,4-dimethylcyclohexane, ω,ω'-diisocyanato-1,4-dimethylbenzene, ω,ω' -Diisocyanato-1,3-dimethylcyclohexane, 1-methyl-2,4-diisocyanatocyclohexane, 4,4'-methylene-bis(isocyanate Cyclohexyl ester), 3-isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate, acid-diisocyanate dimer, ω,ω'-diisocyanatodiethylbenzene , Ω,ω'-diisocyanatodimethyltoluene, ω,ω'-diisocyanatodiethyltoluene, bis(2-isocyanatoethyl) fumarate, 1,4 -Bis(2-isocyanato-prop-2-yl)benzene, and 1,3-bis(2-isocyanato-prop-2-yl)benzene.

Examples of the triisocyanate compound include triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, tris(isocyanatophenyl)-phosphorothioate, and the like.

As a modified polyisocyanate compound derived from the above-mentioned diisocyanate compound As long as it has two or more isocyanate groups, it is not particularly limited. Examples include: biuret structure, isocyanurate structure, urethane structure, uretdione structure, allophanate Polyisocyanate of acid ester structure, trimer structure, etc.; aliphatic isocyanate adduct of trimethylolpropane, etc. In addition, polymeric MDI (MDI=diphenylmethane diisocyanate) can also be used as a polyfunctional isocyanate compound.

The said polyfunctional isocyanate compound can be used individually by 1 type or in combination of 2 or more types.

The isocyanate group possessed by the above-mentioned polyfunctional isocyanate compound may be kept as it is, or may be a blocked isocyanate group blocked by a blocking agent. As the blocking agent, 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4- Pyrazoles such as bromopyrazole and pyrazole; phenols such as phenol, methylphenol, chlorophenol, isobutylphenol, tertiary butylphenol, isoamylphenol, octylphenol, nonylphenol, etc.; ε -Caprolactam, δ-valerolactam, γ-butyrolactam and other internal amides; dimethyl malonate, diethyl malonate, acetone acetone, methyl acetylacetate, Active methylene compounds such as ethyl acetate; oximes such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, acetophenone oxime, diphenyl ketoxime, etc.; imidazole, 2 -Imidazole compounds such as methylimidazole; sodium bisulfite, etc. Among them, from the viewpoint of water repellency, pyrazoles and oximes are preferable.

As the above-mentioned polyfunctional isocyanate compound, it is also possible to use a water-dispersible isocyanate that imparts water-dispersibility to the polyisocyanate by introducing a hydrophilic group into the polyisocyanate structure to give it an interfacial effect. In addition, in order to promote the reaction, conventional catalysts such as organotin and organozinc may also be used in combination.

The above-mentioned crosslinking agent or catalyst can be used individually by 1 type or in combination of 2 or more types.

(fiber)

As the above-mentioned fiber, any one of natural fiber and chemical fiber may be used. Examples of natural fibers include plant fibers such as cotton, hemp, flax, coconut, and rush; animal fibers such as wool, goat hair, mohair, cashmere, camel hair, and silk; mineral fibers such as asbestos. Examples of chemical fibers include inorganic fibers such as rock fiber, metal fiber, graphite, silica, and titanate; rayon, cuproammonium rayon, viscose fiber, multi-brain fiber, refined cellulose fiber, etc. Regenerated cellulose fiber; melt-spun cellulose fiber; protein fiber such as milk protein and soy protein; regenerated silk, alginate fiber, etc. ‧ semi-synthetic fiber; polyamide fiber, polyester fiber, cationic dyeable Synthetic fibers such as polyester fiber, polyvinyl fiber, polyacryl alcohol fiber, polyurethane fiber, polyacrylonitrile fiber, polyethylene fiber, polyvinylidene fiber, and polystyrene fiber. In addition, two or more types of these fibers may be combined (blended, blended, interlaced, interlaced, etc.).

As the above-mentioned polyester fiber, it means: polyethylene terephthalate (PET) fiber, polylactic acid (PLA) fiber, polytrimethylene terephthalate (PTT) fiber, and polyethylene terephthalate (PTT) fiber. Butylene dicarboxylate (PBT) fiber, polypropylene terephthalate (PPT) fiber, polyethylene naphthalate (PEN) fiber, polyarylate fiber, etc. through the reaction of forming ester bonds And the fiber composed of the polymer obtained by condensation. Examples of fibers combined with polyester fibers include synthetic fibers or natural fibers such as cellulose fibers, polyamide fibers, and polyurethane fibers.

The above-mentioned polyamide fiber means a fiber that has polyamide as an essential component and can also be compounded. Examples include nylon 6, nylon 66, nylon 610, nylon 11, nylon 4, nylon 7, and aromatics. Nylon fibers such as nylon (polyaramide). Polyamide is usually obtained by condensation through a reaction that forms an amide bond.

)、衣料品形態的布、地毯、不織 布等之形態。 As the form of the above-mentioned fiber, for example, fiber, woven fabric, braid, cloth, silk, cheese, and yarn (Japanese:

), the form of cloth, carpet, non-woven fabric, etc. in the form of clothing.

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

(Fiber treatment)

As a method of treating the above-mentioned fiber with the above-mentioned treatment liquid, for example, processing methods such as dipping, spraying, coating, etc., or processing methods based on a cleaning method, etc. can be cited. In addition, when the water-repellent composition contains water, it is desirable that after the water-repellent composition is attached to the fibers, the treated fibers are dried in order to remove water.

In the above-mentioned water-repellent fiber product, the adhesion amount of the water-repellent composition on the fiber can be appropriately adjusted according to the required degree of water repellency and durable water repellency. In terms of solid content, the adhesion amount of the water repellent composition is 0.01 to 10 g/m ² , and it is more desirable to adjust it to 0.05 to 5 g/m ² .

After the fiber is treated with the above-mentioned treatment liquid, it is desirable to appropriately perform a heat treatment. The temperature conditions are not particularly limited, but are usually about 110 to 180°C.

In the above-mentioned water-repellent fiber products, especially when it is desired to improve the durable water-repellency, it is desirable to include the above-mentioned step of treating the fiber with the above-mentioned treatment liquid (hereinafter referred to as the water-repellent treatment step) and attaching the above-mentioned crosslinking agent to The process of heating the fiber (hereinafter referred to as the cross-linking step) is the method of water-repellent processing of the fiber.

The crosslinking step includes, for example, the following method: immersing the object to be treated (fiber after the water repellent treatment step) in a liquid obtained by dissolving the crosslinking agent in an organic solvent or emulsifying and dispersing in water, and immersing the The object to be treated is dried to allow the crosslinking agent to adhere, and then heating is performed to cause the crosslinking agent to react with the fiber and the above-mentioned water-repellent composition. In order to fully advance the reaction of the crosslinking 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, if the above-mentioned crosslinking agent is used excessively, there is a risk of impairing the texture. The above-mentioned crosslinking agent is desirably used in an amount of 0.1 to 50% by mass relative to the object (fiber) to be processed, and particularly desirably used in an amount of 0.1 to 10% by mass.

Since the above water-repellent fiber products do not use fluorine-based compounds, they can be regarded as being environmentally friendly. The above water-repellent fiber products have excellent water-repellency, durable water-repellency, and show a soft texture, so they are suitable for down jackets (Japanese: side ground), coats, blousons, windbreakers, blouses, dress shirts, Skirts, trousers, gloves, hats, bedding covers, bedding drying shields, curtains, tents, umbrellas and other clothing items, non-clothing items and other fiber uses.

[Examples]

Hereinafter, the present invention will be described in detail through examples, but the present invention is not limited to these examples. In addition, "parts" and "%" in the examples indicate "parts by mass" and "% by mass" respectively.

<Synthesis of Resin (A)>

Manufacturing example 1

Add 601.2 parts of a mixture of stearic acid and palmitic acid (stearic acid/palmitic acid=65/35 (mass ratio)) into a reaction vessel equipped with a mixer, dehydration tube, condenser tube, thermometer and nitrogen introduction tube, and heat it to melt , Add 207.2 parts of tetraethylenepentamine. After raising the temperature to 180°C in a nitrogen atmosphere, the water produced by the reaction is removed from the system and kept at 180°C~200°C for 3 hours. When the reaction water reaches 39.4 parts by mass, stop heating and proceed. After cooling, an amido resin (1) is obtained. Next, 188.5 parts of capric acid was added to the amido resin (1), and the water generated by the reaction was removed from the system again, and the reaction was performed at 180°C to 200°C for 3 hours to obtain the amido resin (2). After cooling the amide resin (2) to 80°C, Add 15-30 parts of isopropanol relative to 100 parts of resin composition, and further add 1002 parts of ion-exchanged water heated to 80°C and non-ionic surfactant (trade name "Epan 720", Daiichi Kogyo Pharmaceutical Co., Ltd.) Co., Ltd.) 18.8 parts and stirred. Put 202.5 parts of epichlorohydrin as a cationizing agent into the suspended reaction solution, keep the suspension at 80°C to 85°C for about 2 to 4 hours, and then cool to room temperature to obtain resin (A1) The water dispersion.

[Preparation of water repellent composition]

Example 1

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

Examples 2 to 8 and comparative examples 1 to 8

Except that the composition was changed to the composition of Table 1, the same procedure as in Example 1 was used to manufacture.

〔Production of water-repellent fiber products〕

After immersing the water-repellent composition obtained in Example 1 in the treatment liquid (solid content concentration 1%) obtained by diluting with water, the polyester fabric (Polyester Tropical, manufactured by Teijin Co., Ltd.) will adhere to the polyester fabric The polyester fabric of the water-based composition was dried with a circulating air dryer at 180°C for 5 minutes to obtain a water-repellent fiber product. In addition, the adhesion amount of the water-repellent composition to the polyester fabric was 1.3 g/m ² . For each water-repellent composition of Examples 2 to 8 and Comparative Examples 1 to 8, water-repellent fiber products were also produced in the same manner.

The water-repellent fiber products obtained above were evaluated in the following manner.

(Evaluation of Water Repellency of Fiber Products)

According to the spraying method of JIS L 1092 (2009), the spraying water temperature was set to 20°C for testing. The results were evaluated visually according to the following grades.

Water repellency: state

5: There is no wet or adherent surface

4: The surface is slightly adhered and wet

3: The surface shows partly wet

2: The surface shows the wet ones

1: The whole surface shows the wet ones

0: Both the surface and the back surface are completely wet

(Evaluation of Durable Water Repellency of Fiber Products)

The water-repellent fiber product was washed 10 times (HL-10) based on the 103 method of JIS L 0217 (1995), and the water-repellency after air-drying was evaluated in the same manner as the above-mentioned water-repellency evaluation method.

(Texture evaluation of fiber products)

The water-repellent fiber product was evaluated based on the touch of the hand in accordance with the criteria shown below.

×: Hard

△: Slightly hard

○: Soft

◎: Very soft

[Table 1]

The mass parts of each component in Table 1 are values converted from solid content, and the notes and abbreviations in the table are as follows.

※The mass ratio of (A) component and (B) component (calculated as solid content)

(Abbreviations and details of the compound)

X-52-8046: Emulsion of silicone containing long-chain alkyl groups, manufactured by Shin-Etsu Chemical Co., Ltd., with a solid content of 40%

X-51-1302M: MQ resin emulsion, manufactured by Shin-Etsu Chemical Co., Ltd., with a solid content of 17%.

Claims (8)

A water repellent composition, which is characterized by containing resin (A) and silicone (B). The resin (A) is a polyamine (a1) with a secondary amino group and a monocarboxylic acid with a carbon number of 10 to 36 ( a2) and the reactant of epihalohydrin (a3-1) or glycidol (a3-2); The mass ratio ((A)/(B)) of the resin (A) and the silicone (B) is greater than 1 and less than 99 in terms of solid content. The water repellent composition according to claim 1, wherein the component (a1) is the general formula (1): H ₂ N-[(CH ₂ ) _m NH] _n -H (where m represents 1 to 6 N represents an integer from 2 to 6). 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 silicone resin. The water repellent composition according to any one of claims 1 to 5, wherein the (A)/(B) is 3 to 9 in terms of solid content. A water-repellent fiber product characterized by containing fiber and the water-repellent composition according to any one of claims 1 to 6 attached to the fiber. A method for manufacturing a water-repellent fiber product, characterized by comprising a step of treating fibers with a treatment liquid containing the water-repellent composition according to any one of claims 1 to 6.