TW202118851A - Water repellent composition, water-repellent fiber product and method for manufacturing water-repellent fiber product capable of providing a fiber product having excellent water repellency and a good texture - Google Patents

Abstract

This invention provides a non-fluorine-based water repellent composition capable of providing a fiber product having excellent water repellency and a good texture. The water repellent composition of this invention is a dehydration condensate including a 2- to 4-valent polybasic carboxylic acid (a1) and a compound (a2), wherein the compound (a2) is selected from at least one of the group consisting of an alcohol (a2-1) represented by the general formula (1) and an amine (a2-2) represented by the general formula (2).[Chemical 1] R1-OH…(1) (In the formula (1), R1 represents an alkyl group or an alkenyl group having from 6 to 22 carbon atoms.)[Chemical 2] R2-NH-R3….(2)(in the formula (2), R2 and R3 independently represent a hydrogen atom, an alkyl group or an alkenyl group having 6 to 22 carbon atoms, wherein R2 and R3 are not hydrogen atoms at the same time).

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 and therefore unsatisfactory economically, and monomers with fluoroalkyl groups are difficult Decomposability, so there are problems in the environment.

Therefore, in recent years, researches on non-fluorine-based water repellents that do not contain fluorine are being conducted. 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 fiber products treated with a non-fluorine-based water repellent described in Patent Document 1 is still insufficient. 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 that can provide fiber products with excellent water repellency and good texture.

The present inventors conducted intensive studies to solve the above-mentioned problems, and as a result, found that the above-mentioned problems can be solved by a water-repellent composition containing a dehydration condensate of a designated polycarboxylic acid and a designated alcohol or amine, thereby completing the present invention. That is, the present invention relates to the following water repellent composition.

1. A water repellent composition comprising: a dehydration condensate (A) of a two- to four-valent polycarboxylic acid (a1) and a compound (a2), and a silicone (B); the compound (a2) is selected At least one from the group consisting of the alcohol (a2-1) represented by the general formula (1) and the amine (a2-2) represented by the general formula (2).

[化1] R ¹ -OH‧‧‧(1)

(In formula (1), R ¹ represents an alkyl or alkenyl group with 6 to 22 carbon atoms.)

[化2] R ² -NH-R ³ ‧‧‧(2)

(In formula (2), R ² and R ³ each independently represent a hydrogen atom, an alkyl group or alkenyl group having 6 to 22 carbon atoms (the case where both ^{R 2} and R ^{3 are hydrogen atoms is not included).)}

2. The water repellent composition according to the above item 1, wherein the component (a1) contains at least one selected from the group consisting of citric acid, fumaric acid, malic acid, tartaric acid, succinic acid and succinic anhydride Compound.

3. The water-repellent composition according to item 1 or 2, wherein the component (a2) contains selected from palmityl alcohol, stearyl alcohol, distearylamine, dipalmitylamine, stearylamine, palmamine and At least one of the two hardened tallow amines.

4. A water-repellent composition containing the dehydration condensate (A) and silicone (B) as described in any one of the above items 1 to 3.

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

6. The water repellent composition according to item 4 or 5 above, wherein the mass ratio ((A)/(B)) of (A) component to (B) component is greater than 1 and less than 99 in terms of solid content .

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

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

Compared with conventional non-fluorine-based water repellents, the water repellent composition of the present invention can impart superior water repellency to fiber products, and the texture of the fiber products is also good.

〔Water repellent composition〕

The present invention relates to a water-repellent composition containing two to four-valent polycarboxylic acid (a1) (hereinafter referred to as (a1) component.) and compound (a2) (hereinafter referred to as (a2) component). Dehydration condensate (A) (hereinafter referred to as (A) component.), the aforementioned compound (a2) is selected from alcohols (a2-1) represented by general formula (1) described below (hereinafter referred to as (a2-1) component) .) and at least one of the group consisting of the amine (a2-2) represented by the general formula (2) described below (hereinafter referred to as (a2-2) component.).

<Dehydration Condensate (A)>

(a1) The component is not particularly limited as long as it is a divalent, trivalent, or quaternary polycarboxylic acid, and various conventional polycarboxylic acids can be used. (a1) A component can be used individually by 1 type or in combination of 2 or more types.

(a1) The components include, for example, binary, tribasic or quaternary carboxylic acids without functional groups other than carboxyl groups; dibasic, tribasic or quaternary hydroxycarboxylic acids; dibasic, tribasic or tetrabasic carboxylic acids Yuan of amino carboxylic acid and so on.

The above-mentioned binary, tri- or quaternary carboxylic acids without functional groups other than carboxyl groups include, for example, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, Tricarboxylic acid, transaconitic acid, trimellitic acid, etc.

Examples of the above-mentioned di-, tri-, or quaternary hydroxycarboxylic acid include malic acid, tartaric acid, and citric acid. In addition, the above-mentioned divalent, trivalent or quaternary amino carboxylic acid includes, for example, glutamic acid, aspartic acid, and the like.

(a1) A component, and the carboxyl group contained may be an acid anhydride, a chloride, an ester, and an amide, and what is necessary is just to react with the (a2) component mentioned later.

From the viewpoint of excellent water repellency and texture of fiber products, the component (a1) desirably contains at least one compound selected from the group consisting of citric acid, fumaric acid, malic acid, tartaric acid, succinic acid, and succinic anhydride.

(a2-1) The component is not particularly limited as long as it is an alcohol represented by the following general formula (1), and various conventional alcohols can be used. (a2-1) A component can be used individually by 1 type or in combination of 2 or more types.

[化1] R ¹ -OH‧‧‧(1)

(In formula (1), R ¹ represents an alkyl or alkenyl group with 6 to 22 carbon atoms.)

The alcohol represented by the above general formula (1) includes, for example, saturated aliphatics such as hexanol, 2-ethylhexanol, octanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and behenyl alcohol Alcohol; Unsaturated aliphatic alcohols such as oleyl alcohol.

(a2-2) The component is not particularly limited as long as it is an amine represented by the following general formula (2), and various conventional amines can be used. (a2-2) A component can be used individually by 1 type or in combination of 2 or more types.

[化2] R ² -NH-R ³ ‧‧‧(2)

(In formula (2), R ² and R ³ each independently represent a hydrogen atom, an alkyl group or alkenyl group having 6 to 22 carbon atoms (the case where both ^{R 2} and R ^{3 are hydrogen atoms is not included).)}

The amines represented by the above general formula (2) include, for example, primary aliphatic amines such as hexylamine, octylamine, decylamine, palmitamine, and stearylamine; dihexylamine, dioctylamine, didecylamine, and dipalmamine Secondary aliphatic amines such as amine, distearyl amine, di-hardened tallow amine, and bis(docosyl)amine.

(a2) The component (a2-1) and the component (a2-2) may be used together.

From the viewpoint of excellent water repellency and texture of fiber products, (a2) composition It is expected to contain at least one selected from the group consisting of palmityl alcohol, stearyl alcohol, distearylamine, dipalmitylamine, stearylamine, palmitamine, and di-hardened tallowamine. In addition, from the same point of view, More ideally, it contains distearyl amine and di-hardened tallow amine.

<Physical Properties and Manufacturing Method of Dehydration Condensate (A)>

The manufacturing method of (A) component is not specifically limited as long as it is a method of reacting (a1) component and (a2) component, Various conventional methods can be used. Specifically, for example, a method of dehydrating and condensing component (a1) and component (a2) under general reaction conditions of the following reaction. The aforementioned reaction is a reaction in which a carboxylic acid is reacted with an alcohol to esterify a carboxylic acid. Reaction with amine to aminate; for example, considering the boiling point of each component, stirring for 1 to 24 hours at a temperature of about 110 to 180°C under normal pressure or reduced pressure, and dehydration and condensation at the same time The method and so on. In addition, conventional basic or acidic catalysts and solvents can also be used as needed. Furthermore, by using benzene, toluene, xylene, etc. as the solvent, azeotropic dehydration may be used to perform the above-mentioned reaction.

Even when a lower ester of a carboxylic acid or an amide of a carboxylic acid is used as the component (a1), the above-mentioned reaction can proceed in the same manner. Moreover, when transesterification is performed in the above-mentioned reaction, it is desirable to use a catalyst, for example, di-n-butyl tin oxide, p-toluenesulfonic acid, etc. are mentioned.

(A) The usage amount of the (a1) component and (a2) component in the component is not specifically limited.

From the viewpoint of taking into account both the emulsification of component (A) and the water repellency of fiber products, the usage amount of component (a1) and component (a2) in component (A) should ideally be adjusted so that at least the component (a1) One carboxyl group forms an ester bond and/or an amide bond with the component (a2), and at least 0 to one carboxyl group of the component (a1) remains in an unreacted state.

In the case of using a divalent carboxylic acid as the component (a1), take into account (A) From the viewpoint of the emulsification of the components and the water repellency of the fiber product, it is ideal to make the hydroxyl group or the amino group of the component (a2) 1 to 2 equivalents relative to the 2 equivalents of the carboxyl group of the component (a1).

When a trivalent carboxylic acid is used as the component (a1), from the viewpoint of both the emulsification of the component (A) and the water repellency of the fiber product, it is ideal: 3 equivalents to the carboxyl group of the component (a1), The hydroxyl group or amino group of the component (a2) is 2 to 3 equivalents.

In the case of using a quaternary carboxylic acid as the component (a1), from the viewpoint of both the emulsification of the component (A) and the water repellency of the fiber product, it is ideal: 4 equivalents to the carboxyl group of the component (a1), The hydroxyl group or amino group of the component (a2) is 3 to 4 equivalents.

(a1) The unreacted carboxyl group in the component may exist directly as a carboxyl group, or it may form a salt of a carboxyl group. Examples of the carboxyl salt include alkali metal salts such as sodium and potassium; ammonium salts such as ammonia, methylamine, and ethanolamine.

(A) The form of the component is not particularly limited. (A) 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. (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 the component (A) in water in the presence or absence of an emulsifier; or a method of using a commercially available product of an aqueous dispersion of the component (A).

The above-mentioned dispersion method is not particularly limited. The dispersion method includes, for example, a mechanical emulsification method for compulsory emulsification of component (A) and water; reversal emulsification in which water is slowly added to the melt of component (A) to reversely 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 above-mentioned mechanical emulsification method is not particularly limited and can be For example, a homomixer, a high-pressure homogenizer (manufactured by Manton Gaulin), a ball mill, etc. are mentioned.

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 usually in the range of about 1 to 20% 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 amino groups, secondary amino groups, tertiary amino groups, and quaternary ammonium groups. At least one of the cationized starches made of basic nitrogen groups.

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

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-based emulsifier, rosin glycidyl ester acrylate modified anhydride (refer to Japanese Patent Application Publication No. 4-256429), Japanese Patent Application Publication No. 63-23725, Japanese Patent Application Publication No. 63- Various emulsifiers such as emulsifiers described in 240931 and JP 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. In addition, 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.); NewFrontier 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 (Sanyo Chemical Industry Co., Ltd. Company system); Latemul K-180 (manufactured by Kao Co., Ltd.) as its representative examples.

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, rich Dicarboxylic acids such as maleic acid, itaconic acid, muconic acid, and citraconic acid; vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-methyl propane sulfonic acid, (meth)allyl Organic sulfonic acids such as sulfonic acids; or the sodium and potassium salts of various organic acids. Cationic monomer means a monomer having at least one cationic functional group and one vinyl group. Specifically, examples include allylamine; and (meth)acrylic acid N,N-dimethylamine Ethyl, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide Amines and other vinyl monomers with tertiary amine groups or salts of inorganic or organic acids such as hydrochloric acid, sulfuric acid, acetic acid, etc.; or through the use of vinyl monomers containing tertiary amine groups with methyl chloride and chlorine A vinyl monomer containing a quaternary ammonium salt obtained by the reaction of a quaternary chemical such as benzyl sulfate, dimethyl sulfate, epichlorohydrin, etc. Wait. 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- Acrylic acid such as isopropyl (meth)acrylamide, N-tertiary butyl (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, etc. Alkyl esters; allyl-containing monomers such as allyl alcohol; N-substituted acrylamide-based monomers such as isopropylacrylamide; (meth)acrylonitrile, etc.; and Bifunctional vinyl single-system methylenebis(meth)acrylamide, ethylenebis(meth)acrylamide and other bisacrylamide monomers and ethylene glycol di(meth)acrylic acid Diacrylate monomers such as esters, diethylene glycol di(meth)acrylate, diallylamine, divinylbenzene, etc.; as a multifunctional vinyl monomer with 3 or more vinyl groups 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 the component (A) is ideally about 4 to 7, and its appearance is usually white to yellowish white.

<Silicone (B)>

The water-repellent composition of the present invention may further contain silicone (B) (hereinafter referred to as (B) component). By containing the component (B), the above water-repellent composition can impart excellent durable water-repellency (water-repellency of the fiber product after washing) to the fiber product.

(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.

As the above-mentioned monovalent hydrocarbon group, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, 2-ethyl Alkyl groups such as hexyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, hexyl, etc. Alkenyl groups such as alkenyl and cyclohexenyl; aryl groups such as phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, etc.; benzyl, 2-phenethyl, 3-phenylpropyl and other aromatic groups Alkyl groups; or groups in which part or all of the hydrogen atoms of these groups are substituted with 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 groups include alkanes such as methoxy and ethoxy. Oxy etc.

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 silicones containing polyether groups. Ketones, silicones containing long-chain alkyl groups, silicones containing aralkyl groups, silicones containing long-chain alkyl ‧ aralkyl groups, silicones containing higher fatty acid ester groups, silicones containing higher aliphatic amine groups Silicone 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 manufactured by Shin-Etsu Chemical Co., Ltd.); TSF-4709, XF42-B1989 (the above are manufactured by MOMENTIVE PERFORMANCE MATERIALS‧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 a compound having an organic group containing a polyether group in at least any one of the side chain and the end of the silicone structure. Examples of the polyether group include polyoxyalkylenes such as polyoxyethylene, polyoxypropylene, and polyoxyethylene-polyoxypropylene block structures. Examples of commercially available silicones containing polyether groups include: SF8410 (manufactured by Toray Dow Corning Co., Ltd.); KF-6004, KF-6011, KF-6012, KF-6020, KF-6204, X-22- 4515 (the above are made by Shin-Etsu Chemical Industry Co., Ltd.), etc.

The above-mentioned long-chain alkyl-containing silicones can be exemplified by compounds having an organic group containing a long-chain alkyl group in at least any one of the side chain and the terminal of the silicone structure. The above-mentioned long-chain alkyl group is not particularly limited, but from the viewpoint of excellent water repellency and durable water repellency of the fiber product, an alkyl group having 6 or more carbon atoms is preferable, and an alkyl group having 6 to 36 carbon atoms is more preferable. 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 silicones containing long-chain alkyl and aralkyl groups can be exemplified in the silicone structure A compound having an organic group containing the above-mentioned long-chain alkyl group and the above-mentioned aralkyl group in at least any position of the side chain and the terminal. Commercial products of silicone containing long-chain alkyl and aralkyl groups include, for example, SH203 (manufactured by Toray Dow Corning Co., Ltd.); X-22-1877 (manufactured by Shin-Etsu Chemical Co., Ltd.).

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, For example, the same dispersion method and emulsifier as the above-mentioned dispersion method and emulsifier can be mentioned.

<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. Additives include, for example, water repellents, surfactants, defoamers, pH adjusters, antibacterial agents, antifungal agents, coloring agents, antioxidants, deodorants, and various organic other than the above-mentioned water repellent composition. Solvents, chelating agents, antistatic agents, catalysts, crosslinking agents described later, antibacterial deodorants, flame retardants, softeners, anti-wrinkle agents, etc. These additives can be used individually by 1 type or in mixture of 2 or more types.

Examples of the above-mentioned 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; isoamyl stearate , Distearyl succinate, ethylene glycol distearate, butyl stearate and other fatty acid ester defoamers; polyoxyalkylene monool, di-tertiary pentyl phenoxy ethanol, 3-heptane Alcohol-based defoamers such as alcohol and 2-ethylhexanol; ether-based defoamers such as di-tertiary amyl phenoxyethanol, 3-heptyl cyrus, nonyl cyrus, 3-heptyl carbitol, etc. Foaming agent; phosphate defoamers such as tributyl phosphate and tris(butoxyethyl) phosphate; amine defoamers such as dipentylamine; polyalkylene amides, acylate polyamines (acylate polyamine) Isoamide-based defoamers; sulfate-based defoamers such as sodium lauryl sulfate; mineral oil, etc. The antifoaming agent can be used individually by 1 type or in combination of 2 or more types.

Examples of the aforementioned 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, nitric acid, Inorganic acids such as phosphoric acid and boric acid; alkalis such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia, alkanolamine, pyridine, and morpholine. 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 and other ketones; ethyl acetate, methyl acetate, butyl acetate, methyl lactate, ethyl lactate and other esters; diethyl ether, diisopropyl ketone Propyl ether, methyl siloxol, ethyl siloxol, butyl siloxol, dioxane, methyl tertiary butyl ether, butyl carbitol and other ethers; ethylene glycol, diethylene two Alcohol, triethylene glycol, propylene glycol, dipropylene glycol and other glycols; ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether , Propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol and other glycol ethers; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethyl Glycol esters such as glycol monoethyl ether acetate; amides such as formamide, acetamide, benzamide, N,N-dimethylformamide, and acetaniline. 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 type quaternary salts; polyethylene glycol type, polyol esters Type and other nonionic surfactants; imidazoline type quaternary salt, alanine type, betaine type and other amphoteric surfactants; high molecular compound type antistatic polymer; 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 ideally about 4 to 7, and the water repellent composition The appearance is usually white to yellowish white.

The content of the component (A) in the water repellent composition is not particularly limited. From the viewpoint of excellent water repellency, durable water repellency and texture of the fiber product, relative to 100% by mass of the water repellent composition The solid content conversion is ideally about 60 to 100% by mass.

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 0-40% by mass.

The mass ratio ((A)/(B)) of the (A) component and the (B) component in the said water-repellent composition is not specifically limited, Preferably it is more than 1 and less than 99 in solid content conversion. When the above-mentioned mass ratio is greater than 1, the texture of the fiber product becomes better; when the above-mentioned mass ratio is less than 99, the water repellency and durable water repellency of the fiber product become more excellent. From the viewpoint of excellent balance of water repellency, durable water repellency, and texture of the fiber product, the above-mentioned mass ratio is more preferably about 3-9 in terms of solid content.

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 the (A) component and, if necessary, the (B) component and the above-mentioned additives can be cited. 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 above-mentioned 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 can be a compound having a melamine skeleton. Examples include: polymethylol melamine such as trimethylol melamine and hexamethylol melamine; part or all of the methylol groups of polymethylol melamine have carbon Alkoxymethyl melamine with alkoxymethyl group of 1~6; part or all of the methylol group of polymethylol melamine becomes oxymethyl group with 2-6 carbon atoms Methyl melamine and so on. These melamine resins may be any of monomers, dimers or higher polymers, or a mixture of them may also be used. Furthermore, a part co-condensed of urea etc. and melamine can also be used. 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) Co., Ltd. Unika Resin 380K; RIKEN RESIN MM series manufactured by Miki Riken Industry 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; phosphoric acid , Hydrochloric acid, boric acid and other inorganic acids. In these catalysts, organic acids such as citric acid, tartaric acid, malic acid, maleic acid, lactic acid, etc. may be used in combination as a co-catalyst as needed. 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 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, monofunctional (mono)isocyanate compounds such as butyl isocyanate, phenyl isocyanate, toluene isocyanate, naphthyl isocyanate, etc. can be used , Or 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 a conventional polyisocyanate compound can be used. Examples of polyfunctional isocyanate compounds include diisocyanate compounds such as alkylene diisocyanate, aryl diisocyanate, and cycloalkyl diisocyanate; triisocyanate compounds; modified dimers or trimers of the diisocyanate compounds, etc. 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, and 4,4-diphenylmethane diisocyanate. Cyanate, p-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene Group-1,6-diisocyanate, phenylene diisocyanate, toluene diisocyanate or naphthalene diisocyanate, 4,4'-methylene-bis(phenylisocyanate), 2,4'-methylene-bis( Phenyl isocyanate), 3,4'-methylene-bis(phenyl isocyanate), 4,4'-ethylene-bis(phenyl isocyanate), ω,ω'-diisocyanate Cyanato-1,3-dimethylbenzene, 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(cyclohexyl isocyanate), 3-isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate, acid-diisocyanate dimer, ω,ω'- Diisocyanatodiethylbenzene, ω,ω'-diisocyanatodimethyltoluene, ω,ω'-diisocyanatodiethyltoluene, fumaric acid bis(2-isocyanate Ethyl) ester, 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.

The modified polyisocyanate compound derived from the above-mentioned diisocyanate compound is not particularly limited as long as it has two or more isocyanate groups, and examples thereof include a biuret structure, an isocyanurate structure, and urethane Polyisocyanate of acid ester structure, uretdione structure, allophanate structure, trimer structure, etc.; adduct of aliphatic isocyanate of trimethylolpropane. 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 multifunctional 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-hexyl Endoamides, δ-valerolactamide, γ-butyrolactamide and other internal amines; dimethyl malonate, diethyl malonate, acetone, methyl acetylacetate, and acetylacetate Active methylene compounds such as ethyl ester; Oximes such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, acetophenone oxime, diphenyl ketoxime; imidazole, 2-methylimidazole, etc. Imidazole compounds; 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 impart 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; regenerated fibers such as rayon, cuproammonium rayon, viscose fiber, multi-brain fiber, and refined cellulose fiber. Plain fiber; melt-spun cellulose fiber; protein fiber such as milk protein and soy protein; regenerated silk, alginic acid fiber and other regenerated ‧ semi-synthetic fiber; polyamide fiber, polyester fiber, cationic dyeable polyester fiber Dimension, polyvinyl fiber, polyvinyl fiber, polyurethane fiber, polyacrylonitrile fiber, polyethylene fiber, polyvinylidene fiber, polystyrene fiber and other synthetic fibers. 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). Polyamides are usually obtained by condensation reactions that form amide bonds.

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

), fabrics, carpets, non-woven fabrics in the form of clothing products.

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 fibers with the above-mentioned treatment liquid, for example, processing methods such as dipping, spraying, and coating, or processing methods based on a cleaning method, etc. can be cited. In addition, in the above water repellent composition When water is contained, it is ideal to make the water-repellent composition adhere to the above-mentioned fiber, and then dry the treated fiber in order to remove the 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.

Among 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 The above-mentioned fiber is subjected to water-repellent processing by the method of a step of heating the fiber (hereinafter referred to as a cross-linking step).

The cross-linking step includes, for example, a method of immersing the object to be treated (fiber after the water-repellent treatment step) in a liquid obtained by dissolving the cross-linking 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, by heating, the crosslinking agent is reacted with the fiber and the above-mentioned water-repellent composition. In order to make the reaction of the crosslinking agent proceed sufficiently to more effectively improve the durable water repellency, the heating at this time is preferably 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 with respect to the processed object (fiber), and particularly desirably used in an amount of 0.1 to 10% by mass.

The above-mentioned water-repellent fiber products do not use fluorine compounds, so they can be regarded as Environmentally friendly person. 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, jackets (blousons), windbreakers, blouses, dress shirts, skirts , Trousers, gloves, hats, bedding covers, bedding drying covers, curtains, tents or umbrellas and other clothing products, non-clothing products 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.

<Production of dehydration condensate (A)>

Manufacturing example 1

In a reaction device equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, 210 parts (1 mol) of citric acid monohydrate and di-hardened tallow amine (trade name "Armeen 2HT", manufactured by LION SPECIALTY CHEMICALS Co., Ltd.) ) 1000 parts (2 mol) and 1252 parts of toluene are mixed, and the dehydration condensation reaction is continued under reflux of toluene for 20 hours. Toluene was distilled off from this reaction mixture under reduced pressure to obtain a dehydration condensate (A1) containing a diamide compound as a main component (hereinafter referred to as (A1) component). The melting point of the dehydrated condensate is 52~56℃, and the acid value is 55.7mgKOH/g. Next, 400 parts of (A1) component is heated and melted, and 20 parts of anionic surfactant (trade name "HITENOL LA10", manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.) and 1600 parts of warm water (60°C) are mixed, using high pressure The emulsifier emulsifies to prepare an aqueous dispersion of (A1) component with a solid content concentration of 20%.

[Preparation of water repellent composition]

Example 1

100 parts (in terms of solid content) of the aqueous dispersion of the component (A1) obtained in Production Example 1 was used as a water-repellent composition as it was.

Comparative example 1~2

Except for changing the composition 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 Comparative Examples 1 to 2, water-repellent fiber products were also produced in the same manner.

(Evaluation of Water Repellency of Fiber Products)

For the above-mentioned water-repellent fiber products, the spraying method of JIS L 1092 (2009) was used, and the spraying water temperature was set to 20°C for testing. The results were visually evaluated 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

(Texture evaluation of fiber products)

The water-repellent fiber product was evaluated according to the following criteria based on the touch of the hand.

×: 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 abbreviations in the table are as follows.

(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%

[Preparation of water repellent composition]

Example 2

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

Examples 3~9

Except that the composition was changed to the composition of Table 2, the same procedure as in Example 2 was used to manufacture.

〔Production of water-repellent fiber products〕

For each water-repellent composition of Examples 2-9, water-repellent fiber products were also produced in the same manner as described above.

(Evaluation of Water Repellency of Fiber Products)

With respect to the above-mentioned water-repellent fiber product, the water-repellency was evaluated in the same manner as described above.

(Texture evaluation of fiber products)

With respect to the above-mentioned water-repellent fiber product, the texture was evaluated in the same manner as described above.

(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 water-repellency evaluation method.

[Table 2]

The mass parts of each component in Table 2 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 characterized by a dehydration condensate (A) containing a two to four-valent polycarboxylic acid (a1) and a compound (a2), and the compound (a2) is selected from the general formula (1) At least one of the alcohol (a2-1) and the amine (a2-2) represented by the general formula (2); [化1] R ¹ -OH‧‧‧(1) (In formula (1), R ¹ represents an alkyl or alkenyl group with 6 to 22 carbon atoms); [化2] R ² -NH-R ³ ‧‧‧(2) (In formula (2), R ² and R ³ each independently represent a hydrogen atom, an alkyl group or alkenyl group having 6 to 22 carbon atoms (but not including ^{the case where both R 2} and R ³ are hydrogen atoms)). The water repellent composition according to claim 1, wherein the component (a1) contains at least one compound selected from the group consisting of citric acid, fumaric acid, malic acid, tartaric acid, succinic acid, and succinic anhydride. The water-repellent composition according to claim 1 or 2, wherein the component (a2) contains selected from palmityl alcohol, stearyl alcohol, distearyl amine, dipalmityl amine, stearyl amine, palm amine and di-hardened At least one of the groups of tallow amines. A water repellent composition characterized by containing the dehydration condensate (A) and silicone (B) as described in any one of claims 1 to 3. The water repellent composition according to claim 4, wherein the component (B) is a silicone and/or silicone resin containing a long-chain alkyl group. The water repellent composition according to claim 4 or 5, wherein the mass ratio ((A)/(B)) of the (A) component and the (B) component is greater than 1 and less than 99 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.