CN112779772A

CN112779772A - Water repellent composition, water repellent fiber product, and method for producing water repellent fiber product

Info

Publication number: CN112779772A
Application number: CN202011222550.XA
Authority: CN
Inventors: 中川玲; 藤冈大辅; 金滨良
Original assignee: Arakawa Chemical Industries Ltd
Current assignee: Arakawa Chemical Industries Ltd
Priority date: 2019-11-07
Filing date: 2020-11-05
Publication date: 2021-05-11
Also published as: TW202118851A; JP2021075609A; KR20210055609A

Abstract

The invention relates to a water repellent composition, a water repellent fiber product and a method for producing the water repellent fiber product. The invention provides a non-fluorine water repellent composition which can provide a fiber product with excellent water repellency and good texture. A water repellent composition comprising a dehydration condensate (A) of a 2-to 4-membered polycarboxylic acid (a1) and a compound (a2), wherein the compound (a2) is selected from an alcohol (a 2-1) represented by the general formula (1) and an alcohol (a 2-1) represented by the general formula (2)At least 1 of the indicated amines (a 2-2). [ formula 1]R¹-OH (1) (in formula (1), R¹Represents an alkyl group or alkenyl group having 6 to 22 carbon atoms. ) [ chemical formula 2)]R²－NH－R³(2) (in formula (2), R²、R³Each independently represents a hydrogen atom, an alkyl group having 6 to 22 carbon atoms or an alkenyl group (excluding R)²And R³Both in the case of hydrogen atoms). )

Description

Water repellent composition, water repellent fiber product, and method for producing water repellent fiber product

Technical Field

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

Background

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

However, although the fiber product treated with the fluorine-based water repellent exhibits excellent water repellency, the monomer having a fluoroalkyl group is economically unsatisfactory because it is expensive, and the monomer having a fluoroalkyl group is difficult to decompose, which causes environmental problems.

Therefore, in recent years, studies have been made on a non-fluorine water repellent containing no fluorine. For example, patent document 1 proposes a water repellent obtained by emulsifying and dispersing a specific non-fluorine-containing polymer, and patent document 2 proposes a silicone-based water repellent composition containing polyorganosiloxane and a metal alkoxide.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2006-328624

Patent document 2: japanese laid-open patent publication No. 7-305053

Disclosure of Invention

Problems to be solved by the invention

However, the fiber product treated with the non-fluorine-based water repellent described in patent document 1 is insufficient in water repellency in terms of practical use. Further, the silicone-based water repellent agent as in patent document 2 has the following problems: many of the fiber products treated with the composition have insufficient texture.

The invention provides a non-fluorine water repellent composition which can provide a fiber product with excellent water repellency and good texture.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by a water repellent composition comprising a dehydration condensate of a predetermined polycarboxylic acid and a predetermined alcohol or amine, and have completed the present invention. Namely, the present invention relates to the following water repellent composition.

1. A water repellant composition comprising: a dehydration condensate (A) of a 2-to 4-membered polycarboxylic acid (a1) and a compound (a2), and a silicone (B), wherein the compound (a2) is at least 1 selected from an alcohol (a 2-1) represented by general formula (1) and an amine (a 2-2) represented by general formula (2).

[ formula 1]R¹－OH···(1)

(in the formula (1), R¹Represents an alkyl group or alkenyl group having 6 to 22 carbon atoms. )

[ chemical formula 2)]R²－NH－R³···(2)

(in the formula (2), R²、R³Each independently represents a hydrogen atom, an alkyl group having 6 to 22 carbon atoms or an alkenyl group (excluding R)²And R³Both in the case of hydrogen atoms). )

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

3. The water repellent composition according to item 1 or 2, wherein the component (a2) contains at least 1 selected from the group consisting of palmitic alcohol, stearyl alcohol, distearyl amine, dipalmityl amine, stearyl amine, palmityl amine and dihydrotallow amine.

4. A water repellent composition comprising the dehydration condensate (A) according to any one of the above items 1 to 3 and a silicone (B).

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

7. A water repellent fiber product comprising a fiber and the water repellent composition according to any one of items 1 to 6 attached to the fiber.

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

Effects of the invention

The water repellent composition of the present invention can impart excellent water repellency to a textile product and the textile product has a good texture as compared with a conventional non-fluorine-based water repellent.

Detailed Description

[ Water repellent composition ]

The present invention relates to a water repellent composition containing a dehydration condensate (a) (hereinafter referred to as component (a)) of a 2-to 4-membered polycarboxylic acid (a1) (hereinafter referred to as component (a 1)) and a compound (a2) (hereinafter referred to as component (a 2)), wherein the compound (a2) is at least 1 selected from an alcohol (a 2-1) (hereinafter referred to as component (a 2-1)) represented by general formula (1) described later and an amine (a 2-2) (hereinafter referred to as component (a 2-2)) represented by general formula (2) described later.

< dehydration condensate (A) >)

(a1) The component (C) is not particularly limited as long as it is a 2-, 3-or 4-membered polycarboxylic acid, and various known polycarboxylic acids can be used. (a1) The components can be used singly or in combination of 2 or more.

(a1) Examples of the component (A) include: a 2-, 3-or 4-membered carboxylic acid having no functional group other than a carboxyl group; 2-, 3-or 4-membered hydroxycarboxylic acids; 2-, 3-or 4-membered aminocarboxylic acids, and the like.

Examples of the 2-, 3-or 4-membered carboxylic acid having no functional group other than a carboxyl group include malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, malonic acid, aconitic acid, trimellitic acid, and the like.

Examples of the 2-, 3-or 4-membered hydroxycarboxylic acid include malic acid, tartaric acid and citric acid. Examples of the 2-, 3-or 4-membered aminocarboxylic acid include glutamic acid and aspartic acid.

The carboxyl group contained in the component (a1) may be an acid anhydride, acid chloride, ester or amide, as long as it can react with the component (a2) described later.

The component (a1) preferably contains at least 1 compound selected from the group consisting of citric acid, fumaric acid, malic acid, tartaric acid, succinic acid, and succinic anhydride, from the viewpoint of excellent water repellency and texture of a fibrous product.

The component (a 2-1) is not particularly limited as long as it is an alcohol represented by the following general formula (1), and various known alcohols can be used. The component (a 2-1) may be used alone in 1 kind or in combination of 2 or more kinds.

[ formula 1]R¹－OH···(1)

Examples of the alcohol represented by the above general formula (1) include: saturated aliphatic alcohols such as hexanol, 2-ethylhexanol, octanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and behenyl alcohol; unsaturated aliphatic alcohols such as oleyl alcohol.

The component (a 2-2) is not particularly limited as long as it is an amine represented by the following general formula (2), and various known amines can be used. The component (a 2-2) may be used alone in 1 kind or in combination of 2 or more kinds.

[ chemical formula 2)]R²－NH－R³···(2)

Examples of the amine represented by the general formula (2) include: aliphatic primary amines such as hexylamine, octylamine, decylamine, palmitylamine, and stearylamine; and secondary aliphatic amines such as dihexylamine, dioctylamine, didecylamine, dipalmitylamine, distearylamine, dihydrotallow amine, and docosyl amine.

(a2) The component (a 2-1) and the component (a 2-2) may be used in combination.

The component (a2) preferably contains at least 1 selected from the group consisting of palmitol, stearyl alcohol, distearyl amine, dipalmityl amine, stearyl amine, palmityl amine and dihydrotallow amine from the viewpoint of excellent water repellency and texture of the fiber product, and more preferably contains distearyl amine and dihydrotallow amine from the same viewpoint.

< physical Properties of dehydration condensate (A) and method for producing the same

(A) The method for producing component (a) is not particularly limited as long as it is a method of reacting component (a1) and component (a2), and various known methods can be used. Specifically, for example, a method of dehydrating and condensing the component (a1) and the component (a2) under the reaction conditions of esterification by reacting a general carboxylic acid with an alcohol and amidation by reacting a carboxylic acid with an amine, and the like, can be mentioned: the dehydration condensation is carried out while stirring at a temperature of about 110 to 180 ℃ for about 1 to 24 hours under normal pressure or reduced pressure in consideration of the boiling point of each component. In addition, a known basic or acidic catalyst or solvent may be used as necessary. Further, by using benzene, toluene, xylene or the like as the solvent, the above reaction can be carried out by azeotropic dehydration.

The reaction can be carried out in the same manner as in the case where the lower ester of a carboxylic acid or the amide of a carboxylic acid is used as the component (a 1). When the transesterification is carried out in the above reaction, a catalyst is preferably used, and examples thereof include di-n-butyltin oxide and p-toluenesulfonic acid.

(A) The amounts of the component (a1) and the component (a2) used in the component (a) are not particularly limited.

In view of both the emulsifiability of the component (a) and the water repellency of the fibrous product, the amounts of the components (a1) and (a2) in the component (a) are preferably adjusted so that at least 1 carboxyl group of the component (a1) and the component (a2) form an ester bond and/or an amide bond, and at least 0 to 1 carboxyl group of the component (a1) remains unreacted.

When a 2-membered carboxylic acid is used as the component (a1), it is preferable that: the amount of the hydroxyl group or amino group in the component (a2) is 1 to 2 equivalents based on 2 equivalents of the carboxyl group in the component (a 1).

When a 3-membered carboxylic acid is used as the component (a1), it is preferable that: the amount of the hydroxyl group or amino group in the component (a2) is 2 to 3 equivalents based on 3 equivalents of the carboxyl group in the component (a 1).

When a 4-membered carboxylic acid is used as the component (a1), it is preferable that: the hydroxyl group or amino group of the component (a2) is 3 to 4 equivalents relative to 4 equivalents of the carboxyl group of the component (a 1).

(a1) The unreacted carboxyl group in the component (C) may be present as it is in the form of a carboxyl group, or may be a salt of a carboxyl group. As the carboxyl salt, there may be mentioned: alkali metal salts such as sodium and potassium; ammonium salts such as ammonia, methylamine, ethanolamine and the like.

(A) The form of the component (c) is not particularly limited. (A) The component (c) may be used as it is, or may be used as a solution or dispersion obtained by dissolving or dispersing (including suspension and emulsification) the component (c) in a solvent or water. (A) The component (C) is preferably an aqueous dispersion.

(A) The method for producing the aqueous dispersion of the component (a) is not particularly limited, and various known methods can be used. Specific examples thereof include: a method of dispersing the component (a) in water in the presence or absence of an emulsifier; or a commercially available product using an aqueous dispersion of the component (A).

The dispersion method is not particularly limited. Examples of the dispersing method include: a mechanical emulsification method in which the component (A) and water are forcedly emulsified; a phase inversion emulsification method in which water is slowly added to a melt of component (a) to invert an oil phase and a water phase; and a high-pressure emulsification method in which the component (A) is emulsified with water under high pressure. The emulsifying machine used in the above-mentioned mechanical emulsification method is not particularly limited, and examples thereof include a homomixer, a high-pressure homogenizer (manufactured by Manton Gaulin Co., Ltd.), a ball mill, and the like.

The emulsifier is not particularly limited, and various known emulsifiers can be used. Examples of the emulsifier include cationic surfactants, nonionic surfactants, and reactive emulsifiers. The amount of the emulsifier used is usually 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, and the like. Examples of the above cationized starch include: cationized starch in which at least 1 basic nitrogen group selected from primary amino groups, secondary amino groups, tertiary amino groups, and quaternary ammonium groups is incorporated into a molecule of raw starch such as corn, potato, tapioca, wheat, and rice.

Examples of the nonionic surfactant include: polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, sorbitan higher fatty acid esters, polyoxyethylene higher fatty acid esters, glycerin higher fatty acid esters, block copolymers of polyalkylene oxides, and the like, and specific examples thereof include: polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene styrylphenyl ether, sorbitan monolaurate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene monooleate, oleic acid monoglyceride, stearic acid monoglyceride, polyoxyethylene-polyoxypropylene-block copolymer, and the like.

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

Examples of the reactive emulsifier include: a polyoxyethylene alkyl ether having at least 1 functional group containing a double bond capable of radical polymerization in the molecule, a sulfosuccinate salt of a polyoxyethylene alkyl ether having at least 1 functional group in the molecule, a sulfate salt of a polyoxyethylene alkyl ether having at least 1 functional group in the molecule, a polyoxyethylene phenyl ether having at least 1 functional group in the molecule, a sulfosuccinate salt of a polyoxyethylene phenyl ether having at least 1 functional group in the molecule, a sulfate salt of a polyoxyethylene phenyl ether having at least 1 functional group in the molecule, a polyoxyethylene alkylphenyl ether having at least 1 functional group in the molecule, a sulfosuccinate salt of a polyoxyethylene alkylphenyl ether having at least 1 functional group in the molecule, a sulfate salt of a polyoxyethylene alkylphenyl ether having at least 1 functional group in the molecule, a sulfuric acid salt of a polyoxyethylene alkylphenyl ether having, Polyoxyethylene aralkyl phenyl ether having at least 1 of the functional groups in the molecule, sulfosuccinate ester salt of polyoxyethylene aralkyl phenyl ether having at least 1 of the functional groups in the molecule, sulfate ester salt of polyoxyethylene aralkyl phenyl ether having at least 1 of the functional groups in the molecule, phosphate ester salt of polyoxyethylene alkyl phenyl ether having at least 1 of the functional groups in the molecule, aliphatic or aromatic carboxylate salt of polyoxyethylene alkyl phenyl ether having at least 1 of the functional groups in the molecule, examples of the emulsifier include acid phosphoric acid (meth) acrylate emulsifiers and acid anhydride-modified rosin glycidyl ester acrylates (see JP-A-4-256429), and emulsifiers described in JP-A-63-23725, JP-A-63-240931 and JP-A-62-104802.

Further, there may be mentioned a reactive emulsifier obtained by substituting polyoxyethylene in the above reactive emulsifier with polyoxypropylene or a block copolymer or a random copolymer of polyoxyethylene and polyoxypropylene. Examples of commercially available products thereof include: KAYAMER PM-1, KAYAMER PM-2, and KAYAMER PM-21 (manufactured by Nippon Chemicals, Inc.); SE-10N, NE-10, NE-20, NE-30, ADEKA REASOAP SR-10, ADEKA REASOAP SR-20, and ADEKA REASOAP ER-20 (manufactured by ADEKA, Inc.); new Frontier A229E, New Frontier N117E, New Frontier N250Z, AQUALON RN-10, AQUALON RN-20, AQUALON RN-50, AQUALON HS-10, AQUALON KH-05, and AQUALON KH-10 (manufactured by first Industrial pharmaceutical Co., Ltd.); eleminol JS-2 (manufactured by Sanyo chemical industries, Ltd.); latex K-180 (manufactured by Kao corporation) and the like are typical examples thereof.

The emulsifier is preferably a cationic surfactant or a nonionic surfactant.

The protective colloid may be used as needed. The protective colloid is not particularly limited, and a known protective colloid can be used. Specifically, for example, a colloid obtained by polymerizing an anionic monomer, a cationic monomer, and other monomers is included. The anionic monomer is a monomer having at least 1 anionic functional group and 1 vinyl group, and specific examples thereof include: monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, muconic acid, and citraconic acid; organic sulfonic acids such as vinylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and (meth) allylsulfonic acid; or sodium salts and potassium salts of the above organic acids. The cationic monomer is a monomer having at least 1 cationic functional group and 1 vinyl group, and specific examples thereof include: allyl amine; and vinyl monomers having a tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, N-dimethylaminopropyl (meth) acrylamide, N-diethylaminopropyl (meth) acrylamide, and salts of inorganic or organic acids such as hydrochloric acid, sulfuric acid, and acetic acid thereof, or vinyl monomers containing a quaternary ammonium salt obtained by reacting the vinyl monomer having a tertiary amino group with a quaternizing agent such as methyl chloride, benzyl chloride, dimethyl sulfuric acid, and epichlorohydrin. Examples of the monomer other than the anionic monomer and the cationic monomer include: alkyl acrylates such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-diisopropyl (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; allyl monomers containing allyl groups such as allyl alcohol; n-substituted acrylamide monomers such as isopropylacrylamide; (meth) acrylonitrile, etc.; and bisacrylamide-based monomers such as methylenebis (meth) acrylamide and ethylenebis (meth) acrylamide, diacrylate-based monomers such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, diallylamine, divinylbenzene, and the like as 2-functional vinyl monomer systems; examples of the polyfunctional vinyl monomer having 3 or more vinyl groups include 1,3, 5-triacryloylhexahydro-s-triazine, triallylisocyanurate, triallylamine, and tetramethylolmethane tetraacrylate. The polymerization method may be any known method such as a radical polymerization method.

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

(A) The physical properties of the aqueous dispersion of the component (c) are not particularly limited. The concentration of the aqueous dispersion of component (A) is preferably about 0.1 to 50% by weight as a solid content in view of handling and the like. The aqueous dispersion of component (A) preferably has a volume average particle diameter of about 0.2 to 10 μm in view of dispersibility. The pH of the aqueous dispersion of component (A) is preferably about 4 to 7, and the aqueous dispersion has an appearance of generally white to yellowish white.

< Silicone (B) >

The water repellent composition of the present invention may further contain a silicone (B) (hereinafter referred to as component (B)). The water repellent composition can impart excellent durable water repellency (water repellency of a washed textile) to a textile by containing the component (B).

(B) The component (c) is not particularly limited, and various known silicones can be used. (B) The components can be used singly or in combination of 2 or more.

(B) Examples of the component (B) include silicone resins and silicone oils.

(Silicone resin)

The silicone resin is not particularly limited. Examples of the silicone resin include: an organopolysiloxane having a three-dimensional structure that contains a T unit and/or a Q unit as constituent components and contains at least 1 siloxane unit selected from an M unit and a D unit as constituent units other than the T unit and/or the Q unit. The M unit, the D unit, the T unit, and the Q unit are (R)₃SiO_1/2Unit, (R)₂SiO_2/2Cell, RSiO_3/2Unit andSiO_4/2and (4) units.

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

Examples of the monovalent hydrocarbon group include: alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, hexenyl, cyclohexenyl and the like; aryl groups such as phenyl, tolyl, xylyl, α -naphthyl and β -naphthyl; aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl; or a group in which some or all of the hydrogen atoms of these groups are substituted with a halogen atom such as F, Cl or Br, a cyano group or the like (for example, 3-chloropropyl, 3,3, 3-trifluoropropyl, 2-cyanoethyl or the like).

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

Examples of the silicone resin include: an MQ resin containing the M unit and the Q unit as main components; a TD resin containing the T unit and the D unit as main components; an MT resin containing the M unit and the T unit as main components; an MDQ resin composed of the M unit, the D unit and the Q unit; an MDT resin comprising the M unit, the D unit and the T unit; and MDTQ resin composed of the M unit, D unit, T unit, and Q unit.

Examples of commercially available products of the 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 industries, Ltd.); SD-7292, BY 24-843, MQ-1600, MQ-1640 (manufactured BY Tooli-Dow Corning Co., Ltd.), etc.

(Silicone oil)

The silicone oil is not particularly limited. Examples of the silicone oil include linear organopolysiloxanes. Examples of such organopolysiloxanes include: an organopolysiloxane having an organic group at least one of a side chain and a terminal thereof.

Examples of the silicone oil include ordinary silicone (Japanese: ストレートシリコーン) and modified silicone.

Examples of the common silicone include dimethyl silicone, methylphenyl silicone, and methylhydrogen silicone.

Examples of the modified silicone include: amino group-containing silicones, epoxy group-containing silicones, carbinol group-containing silicones, mercapto group-containing silicones, carboxyl group-containing silicones, polyether group-containing silicones, long-chain alkyl group-containing silicones, aralkyl group-containing silicones, long-chain alkyl-aralkyl group-containing silicones, higher fatty acid ester group-containing silicones, higher aliphatic amide group-containing silicones, and the like.

Examples of the amino group-containing silicone include: and compounds having an organic group containing an amino group and/or an imino group at least one of a side chain and a terminal of the siloxane structure. Examples of commercially available amino group-containing silicones include: WACKER FINISH WR301, WR1100, WR1200, WR1300, WR1600 (manufactured by Asahi Kasei corporation); KF8005, KF-868, KF-864, KF-393, KF-8021 (manufactured by shin-Etsu chemical industries, Ltd.); TSF-4709, XF 42-B1989 (manufactured by MOMENTIVE PERFOMANCE MATERIALS JAPAN, supra); BY 16-872, SF-8417, BY 16-853U, BY 16-892 (manufactured BY Tollio-daokning Co., Ltd.), and the like.

Examples of the epoxy group-containing silicone include: and compounds having an organic group containing an epoxy group at least one of a side chain and a terminal of the siloxane structure. Examples of commercially available epoxy group-containing silicones include X-22-343, KF-101, KF-1001, X-22-163A, X-22-163B, X-22-163C, KF-105, X-22-169 AS, X-22-169B, X-22-173 BX, and X-22-173 DX (manufactured by shin-Etsu chemical Co., Ltd.).

Examples of the above-mentioned carbinol group-containing silicone include: and compounds having an organic group containing a carbinol group at least one of the side chain and the terminal of the siloxane structure. Examples of commercially available products of carbinol group-containing silicone include X-22-4039, X-22-4015, X-22-170 BX, X-22-170 DX, KF-6000, KF-6001, KF-6002, and KF-6003 (manufactured by shin-Etsu chemical industries, Ltd.).

Examples of the mercapto group-containing silicone include: and compounds having a mercapto group-containing organic group at least one of the side chain and the terminal of the siloxane structure. Commercially available products of mercapto group-containing silicone include, for example, KF-2001, KF-2004 and X-22-167B, X-22-167C (manufactured by shin-Etsu chemical Co., Ltd.).

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

Examples of the polyether group-containing silicone include: and compounds having an organic group containing a polyether group at least one of a side chain and a terminal of a siloxane structure. Examples of the polyether group include polyoxyalkylenes such as polyoxyethylene, polyoxypropylene, and a polyoxyethylene-polyoxypropylene block structure. Commercially available silicone containing polyether groups include, for example: SF8410 (manufactured by dongli-daokning corporation); KF-6004, KF-6011, KF-6012, KF-6020, KF-6204, X-22-4515 (manufactured by shin-Etsu chemical Co., Ltd.), and the like.

Examples of the long-chain alkyl group-containing silicone include: and compounds having an organic group containing a long-chain alkyl group at least one of a side chain and a terminal of the siloxane structure. The long chain alkyl group is not particularly limited, but is preferably an alkyl group having 6 or more carbon atoms, more preferably an alkyl group having 6 to 36 carbon atoms, in view of excellent water repellency and durable water repellency of the fiber product. Commercially available products of silicone containing a long-chain alkyl group include, for example: SF8416 (manufactured by dongli-daokning corporation); KF-412, KF-413, KF-414, KF-415, KF-4003, KF-4701, KF-4917, KF-7235B, X-22-1877, X-52-8046 (manufactured by shin-Etsu chemical industries, Ltd.), and the like.

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

Examples of the long-chain alkyl-aralkyl group-containing silicone include: and compounds having an organic group containing the long-chain alkyl group and the aralkyl group at least one of the side chain and the terminal of the siloxane structure. Commercially available products of long-chain alkyl-aralkyl group-containing silicones include, for example: SH203 (manufactured by dongli-daokning corporation); x-22-1877 (manufactured by shin-Etsu chemical Co., Ltd.), and the like.

The above-mentioned silicone containing higher fatty acid ester groups can be exemplified by: and compounds having an organic group containing a higher fatty acid ester group at least one of the side chain and the terminal of the siloxane structure. Examples of commercially available products of higher fatty acid ester group-containing silicones include X-22-715 (manufactured by shin-Etsu chemical Co., Ltd.).

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

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

(B) The form of the component (c) is not particularly limited. (B) The component (c) may be used as it is, or may be used in the form of a solution or dispersion obtained by dissolving or dispersing (including suspension or emulsification) the component (c) in a solvent or water. (B) The component (C) is preferably an aqueous dispersion.

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

< additive >

The water repellent composition may contain various known additives as needed, as long as the effects of the present invention are not impaired. Examples of the additives include water-repellent agents other than the water-repellent agent composition, surfactants, antifoaming agents, pH adjusters, antibacterial agents, antifungal agents, coloring agents, antioxidants, deodorizing agents, various organic solvents, chelating agents, antistatic agents, catalysts, crosslinking agents, antibacterial and deodorant agents, flame retardants, softening agents, and wrinkle reducing agents. The above additives may be used singly in 1 kind or in combination of 2 or more kinds.

Examples of the defoaming agent include: grease-based antifoaming agents such as castor oil, sesame oil, linseed oil, animal and vegetable oils, and the like; fatty acid defoaming agents such as stearic acid, oleic acid and palmitic acid; fatty acid ester-based antifoaming agents such as isoamyl stearate, distearyl succinate, ethylene glycol distearate and butyl stearate; alcohol defoaming agents such as polyoxyalkylene monool, di-t-pentylphenoxyethanol, 3-heptanol, and 2-ethylhexanol; ether defoaming agents such as di-t-amyl phenoxyethanol, 3-heptyl cellosolve, nonyl cellosolve, 3-heptyl carbitol and the like; phosphate ester defoaming agents such as tributyl phosphate and tris (butoxyethyl) phosphate; amine defoaming agents such as dipentylamine; amide-based antifoaming agents such as polyalkylene amides and acylated polyamines (Japanese: アシレートポリアミン); sulfate-based antifoaming agents such as sodium lauryl sulfate; mineral oil, etc. The defoaming agent may be used alone in 1 kind or in combination of 2 or more kinds.

Examples of the pH adjuster 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; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, and the like; and bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia, alkanolammonium, pyridine, morpholine, and the like. The pH adjusting agent may be used alone in 1 kind or in combination of 2 or more kinds.

Examples of the organic solvent include: aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol, isopropanol, isobutanol, hexanol, 2-ethylhexanol and the like; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and diacetone alcohol; esters such as ethyl acetate, methyl acetate, butyl acetate, methyl lactate, and ethyl lactate; ethers such as diethyl ether, diisopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, dioxane, methyl tert-butyl ether, and butyl carbitol; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol; glycol ethers such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, and 3-methoxy-3-methyl-1-butanol; glycol esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate; amides such as formamide, acetamide, benzamide, N-dimethylformamide, and acetanilide. The organic solvent may be used alone in 1 kind or in combination of 2 or more kinds.

As the antistatic agent, an antistatic agent having a property of hardly inhibiting water repellency is preferably used. Examples of antistatic agents include: cationic surfactants such as higher alcohol sulfate, sulfated oil, sulfonate, quaternary ammonium salts, and imidazoline type quaternary salts; nonionic surfactants such as polyethylene glycol type and polyol ester type; amphoteric surfactants of imidazoline type quaternary salts, alanine type, betaine type, and the like; high molecular compound type antistatic polymers; polyalkylamines, and the like. The antistatic agent may be used singly in 1 kind or in combination of 2 or more kinds.

[ Properties and production method of Water repellent composition ]

The physical properties of the water repellent composition are not particularly limited. The concentration of the water repellent composition is preferably about 0.1 to 50% by weight in terms of handling and the like. In addition, the water repellent composition preferably has a volume average particle diameter of about 0.2 to 10 μm in view of dispersibility. The pH of the water repellent composition is preferably about 4 to 7, and the water repellent composition is generally white to yellowish white in appearance.

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

The content of the component (B) in the water repellent composition is not particularly limited, and is preferably about 0 to 40% by mass in terms of solid content with respect to 100% by mass of the water repellent composition, from the viewpoint of excellent water repellency, durable water repellency, and texture of a textile product.

The mass ratio ((a)/(B)) of the component (a) to the component (B) in the water repellent composition is not particularly limited, and is preferably more than 1 and less than 99 in terms of solid content. When the mass ratio is more than 1, the texture of the textile product becomes better, and when the mass ratio is less than 99, the water repellency and durable water repellency of the textile product become more excellent. The mass ratio is preferably about 3 to 9 in terms of solid content, from the viewpoint of excellent balance among water repellency, durable water repellency, and texture of the fiber product.

The method for producing the water repellent composition of the present invention is not particularly limited, and various known methods can be used. Specifically, for example, a method of mixing the component (a) and, if necessary, the component (B) and the additives is mentioned. The order of mixing the components is not particularly limited, and mixing may be started from any component. The mixing method is also not particularly limited, and various known methods such as stirring can be used.

[ Water-repellent fiber product ]

The water-repellent fiber product of the present invention is obtained by treating a fiber with a treatment liquid containing the water-repellent composition.

(treatment solution)

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

The aqueous medium is preferably water or a mixed solvent of water and a hydrophilic solvent miscible with water, for example. Examples of the hydrophilic solvent include methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, hexylene glycol, glycerin, ethylene glycol butyl ether, diethylene glycol butyl ether, Solfit (Japanese: ソルフィット), N-methylpyrrolidone, dimethylformamide, and dimethyl sulfoxide.

(crosslinking agent)

The above-mentioned treatment liquid may further contain a crosslinking agent for the purpose of improving durable water repellency of the water-repellent fiber product. Examples of the crosslinking agent include melamine resins and compounds having 1 or more isocyanate groups or blocked isocyanate groups.

As the melamine resin, a compound having a melamine skeleton can be used, and examples thereof include: polyhydroxylmethylmelamines such as trimethylol melamine and hexamethylolmelamine; an alkoxymethyl melamine wherein some or all of the methylol groups of the polymethylol melamine are converted to alkoxymethyl groups having an alkyl group having 1 to 6 carbon atoms; and acyloxymethylmelamine in which a part or all of the methylol groups of the polymethylolmelamine are acyloxymethyl groups having acyl groups having 2 to 6 carbon atoms. These melamine resins may be any of monomers or polymers of two or more monomers, or may be a mixture thereof. Further, urea or the like may be co-condensed with a part of melamine. Examples of such melamine resins include: BECKAMINE APM, BECKAMINE M-3 (60), BECKAMINE MA-S, BECKAMINE J-101, and BECKAMINE J-101 LF, available from DIC corporation; unika Resin 380K manufactured by Unichemical industries; RIKEN RESIN MM series manufactured by Sanzhi research industries, Ltd.

From the viewpoint of promoting the reaction, a catalyst is preferably used for the melamine resin. The catalyst is not particularly limited as long as it is a catalyst generally used, and examples thereof include borofluorides 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, and boric acid. These catalysts may be used together with an organic acid such as citric acid, tartaric acid, malic acid, maleic acid or lactic acid as a co-catalyst, if necessary. Examples of such catalysts include: catalyst ACX, Catalyst 376, Catalyst O, Catalyst M, Catalyst G (GT), Catalyst X-110, Catalyst GT-3, and Catalyst NFC-1, available from DIC corporation; unika Catalyst 3-P and Unika Catalyst MC-109, manufactured by Union chemical industries; riken Fixer RC series, Riken Fixer MX series, and Riken Fixer RZ-5, all available from Sanjiu research industries, Ltd.

As the compound having 1 or more isocyanate groups or blocked isocyanate groups, a monofunctional (mono) isocyanate compound or a polyfunctional isocyanate compound such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate or naphthyl isocyanate can be used.

The polyfunctional isocyanate compound is not particularly limited as long as it has 2 or more isocyanate groups in the molecule, and a known polyisocyanate compound can be used. Examples of the polyfunctional isocyanate compound include: diisocyanate compounds such as alkylene diisocyanate, aryl diisocyanate and cycloalkyl diisocyanate; triisocyanate compound, and modified polyisocyanate compounds such as dimer or trimer of the diisocyanate compound. The number of carbon atoms of the alkylene diisocyanate is preferably 1 to 12.

Examples of the diisocyanate compound include: 2, 4-or 2, 6-tolylene 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, phenylene diisocyanate, toluene diisocyanate, 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), omega '-diisocyanato-1, 3-dimethylbenzene, omega' -diisocyanato-1, 4-dimethylcyclohexane, omega '-diisocyanato-1, 4-dimethylbenzene, omega' -diisocyanato-1, 3-dimethylcyclohexane, 1-methyl-2, 4-diisocyanatocyclohexane, 4 '-methylene-bis (cyclohexylisocyanate), 3-isocyanato-methyl-3, 5, 5-trimethylcyclohexylisocyanate, acid-diisocyanate dimer, omega' -diisocyanatodiethylbenzene, omega '-diisocyanatodimethyltoluene, omega' -diisocyanatodiethyltoluene, bis (2-isocyanatoethyl) fumarate, 1, 4-bis (2-isocyanato-propan-2-yl) benzene and 1, 3-bis (2-isocyanato-propan-2-yl) benzene.

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

The modified polyisocyanate compound derived from the diisocyanate compound is not particularly limited as long as it has 2 or more isocyanate groups, and examples thereof include: polyisocyanates having a biuret structure, an isocyanurate structure, a urethane structure, a uretdione structure, an allophanate structure, a trimer structure, etc.; adducts of aliphatic isocyanates of trimethylolpropane. In addition, polymeric MDI (MDI ═ diphenylmethane diisocyanate) can also be used as the polyfunctional isocyanate compound.

The polyfunctional isocyanate compound may be used alone in 1 kind or in combination of 2 or more kinds.

The isocyanate group of the polyfunctional isocyanate compound may be left as it is, or may be a blocked isocyanate group blocked with a blocking agent. Examples of the blocking agent include: pyrazoles such as 3, 5-dimethylpyrazole, 3-methylpyrazole, 3, 5-dimethyl-4-nitropyrazole, 3, 5-dimethyl-4-bromopyrazole and pyrazole; phenols such as phenol, methylphenol, chlorophenol, isobutylphenol, tert-butylphenol, isopentylphenol, octylphenol, and nonylphenol; lactams such as epsilon-caprolactam, delta-valerolactam and gamma-butyrolactam; active methylene compounds such as dimethyl malonate, diethyl malonate, acetylacetone, methyl acetoacetate, and ethyl acetoacetate; oximes such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; imidazole compounds such as imidazole and 2-methylimidazole; sodium bisulfite and the like. Among them, pyrazoles and oximes are preferable from the viewpoint of water repellency.

As the above polyfunctional isocyanate compound, there can also be used: water-dispersible isocyanates in which water is dispersed are imparted to polyisocyanates by introducing hydrophilic groups into the polyisocyanate structure to impart a surface active effect thereto. In addition, a known catalyst such as organic tin, organic zinc, or the like may be used in combination to accelerate the reaction.

The crosslinking agent and the catalyst may be used singly or in combination of 1 or more.

(fiber)

The fibers may be natural fibers or chemical fibers. Examples of natural fibers include: plant fibers of cotton, hemp, flax, coconut, rush, etc.; animal fibers such as wool, goat wool, mohair, cashmere, camel hair, silk, etc.; inorganic fibers such as asbestos. Examples of the chemical fibers include: inorganic fibers such as rock fibers (Japanese: ロックファィバ -), metal fibers, graphite, silica, and titanates; regenerated cellulose fibers such as rayon, cuprammonium fibers, viscose, polynosic fibers, and refined cellulose fibers; melt spinning cellulose fibers; protein fibers such as milk protein and soybean protein; regenerated semi-synthetic fibers such as regenerated silk and alginic acid fiber; synthetic fibers such as polyamide fibers, polyester fibers, cationic dyeable polyester fibers, polyethylene fibers, polypropylene alcohol fibers, polyurethane fibers, acrylic fibers, polyethylene fibers, polyvinylidene fibers, polystyrene fibers, and the like. These fibers may be combined (blended, mixed, interwoven, cross-knitted, etc.) by2 or more.

The polyester fiber is represented by: polyethylene terephthalate (PET) fibers; and fibers composed of polymers obtained by condensation through a reaction of forming an ester bond, such as polylactic acid (PLA) fibers, polytrimethylene terephthalate (PTT) fibers, polybutylene terephthalate (PBT) fibers, polytrimethylene terephthalate (PPT) fibers, polyethylene naphthalate (PEN) fibers, and polyarylate fibers. Examples of the fibers to be combined with the polyester fibers include synthetic fibers such as cellulose fibers, polyamide fibers, and polyurethane fibers, and natural fibers.

The polyamide fiber is a fiber containing polyamide as an essential component and may be a composite fiber, and examples thereof include nylon fibers such as nylon 6, nylon 66, nylon 610, nylon 11, nylon 4, nylon 7, and aromatic nylon (aramid). Polyamides are generally obtained by condensation through amide bond formation reactions.

Examples of the form of the fiber include fibers, woven fabrics, knitted fabrics, filaments, cheese, yarn-formed yarn (japanese patent application No. かせ), cloth in the form of clothing, carpet (japanese patent application No. カーペット), and nonwoven fabrics.

The water repellent composition of the present invention is preferably used for cotton, nylon fibers, polyester fibers, or composite fibers of 2 or more of these.

(fiber treatment)

Examples of the method for treating the fibers with the treatment liquid include a processing method such as dipping, spraying, or coating, and a processing method by a cleaning method. In addition, when the water repellent composition contains water, it is preferable that: after the water-repellent composition is attached to the fibers, the treated fibers are dried to remove water.

In the water-repellent fiber product, the amount of the water-repellent composition attached to the fibers may be appropriately adjusted depending on the degree of water repellency and durable water repellency required, and is preferably adjusted to the fibers in terms of solid contentThe amount of the water repellent composition to be adhered is 0.01 to 10g/m in terms of the amount of the water repellent composition²Is adjusted in a manner of (1), more preferably to 0.05 to 5g/m²The manner of (2) is adjusted.

After the fibers are treated with the treatment liquid, the fibers are preferably appropriately heat-treated. The temperature is not particularly limited, but is usually about 110 to 180 ℃.

In the water-repellent fiber product, particularly when it is intended to improve durable water repellency, it is preferable to perform water repellent processing on the fibers by a method including the step of treating the fibers with the treatment liquid (hereinafter referred to as a water-repellent treatment step) and the step of adhering the crosslinking agent to the fibers and heating the fibers (hereinafter referred to as a crosslinking step).

Examples of the crosslinking step include the following methods: the water repellent composition is prepared by impregnating a material to be treated (fibers after the water repellent treatment step) in a liquid obtained by dissolving the crosslinking agent in an organic solvent or emulsifying and dispersing the crosslinking agent in water, drying the impregnated material to adhere the crosslinking agent, and then heating the resultant to react the crosslinking agent with the fibers and the water repellent composition. In order to sufficiently carry out the reaction of the crosslinking agent and to more effectively improve the durable water repellency, the heating is preferably carried out at 110 to 180 ℃ for 1 to 5 minutes.

In addition, if the crosslinking agent is used excessively, there is a risk of impairing the texture. The crosslinking agent is preferably used in an amount of 0.1 to 50% by mass, particularly preferably 0.1 to 10% by mass, based on the treated material (fiber).

The water repellent fiber product is environmentally friendly because it does not use a fluorine compound. The water-repellent fiber product has excellent water repellency and durable water repellency, and exhibits a soft texture, and is therefore suitable for fiber applications such as down jackets (japanese: side), coats, jackets, coats, gowns, shirts, skirts, pants, gloves, hats, bedding covers, bedding drying covers, curtains, clothing articles such as tents and umbrellas, and non-clothing articles.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, "part" and "%" represent "part by mass" and "% by mass", respectively.

< production of dehydrated condensate (A) >

Production example 1

In a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube, 210 parts (1 mol) of citric acid monohydrate, 1000 parts (2 mol) of dihydrotallow amine (trade name "Armeen 2 HT", manufactured by LION SPECIALTY CHEMICALS, ltd.) and 1252 parts of toluene were mixed, and dehydration condensation reaction was continued for 20 hours under reflux of toluene. Toluene was distilled off from the reaction mixture under reduced pressure to obtain a dehydration condensate (a1) (hereinafter referred to as (a 1)) containing a diamide compound as a main component. The dehydration condensate has a melting point of 52 to 56 ℃ and an acid value of 55.7 mgKOH/g. Subsequently, 400 parts of component (a1) was melted by heating, and 20 parts of an anionic surfactant (trade name "HITENOL LA 10", manufactured by seiko corporation) and 1600 parts of warm water (60 ℃) were mixed and emulsified by a high-pressure emulsifier to prepare an aqueous dispersion of component (a1) having a solid content 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 it is as a water repellent composition.

Comparative examples 1 to 2

The production was carried out by the same procedure as in example 1, except that the composition was changed to the composition shown in table 1.

[ production of Water-repellent fiber product ]

After a Polyester fabric (manufactured by Polyester thermoplastic imperial corporation) was impregnated in a treatment liquid (solid content concentration 1%) obtained by diluting the water repellent composition obtained in example 1 with water, the Polyester fabric having the water repellent composition adhered thereto was dried at 180 ℃ for 5 minutes by an air-circulating dryer, thereby obtaining a water repellent fiber product. Here, the amount of the water-repellent composition attached to the polyester fabric was 1.3g/m². Comparative examples 1 to 2Water-repellent fiber products were also produced in the same manner as in the respective water-repellent composition.

(evaluation of Water repellency of fiber product)

The water-repellent fiber product was tested by a spraying method according to JIS L1092 (2009) with the spraying water temperature set at 20 ℃. The results were visually evaluated on the following scale.

Water repellency: status of state

5: no adhesion and wetting on the surface

4: slightly moist and adherent surface

3: surface showing partial wetting

2: surface showing wetting

1: the whole surface showed wetting

0: both the front and back sides showed complete wetting

(evaluation of texture of fiber product)

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

X: hard

And (delta): is slightly hard

O: softness

Very good: is very soft

[ Table 1]

The parts by mass of each component in table 1 are values in terms of solid content, and abbreviations in the table are as follows.

(abbreviation and details of Compound)

X-52-8046: the emulsion containing silicone with long chain alkyl has a solid content of 40%

X-51-1302M: the solid content of MQ resin emulsion manufactured by shin-Etsu chemical industry (Ltd.) is 17%

[ preparation of Water repellent composition ]

Example 2

A water repellent composition having a solid content of 15% was prepared by mixing 60 parts (in terms of solid content) of the aqueous dispersion of component (a1) obtained in production example 1 and 40 parts (in terms of solid content) of an emulsion (trade name "X-52-8046" manufactured by shin-Etsu chemical industries, Ltd.) of silicone containing a long chain alkyl group as component (B) (the solid content concentration was 40%).

Examples 3 to 9

The same procedure as in example 2 was used to produce the polycarbonate resin composition, except that the composition was changed to the composition shown in table 2.

[ production of Water-repellent fiber product ]

Water-repellent fiber products were also produced in the same manner as described above for each of the water-repellent agent compositions of examples 2 to 9.

(evaluation of Water repellency of fiber product)

The water repellency of the water-repellent fiber product was evaluated in the same manner as described above.

(evaluation of texture of fiber product)

The texture of the water-repellent fiber product was evaluated in the same manner as described above.

(evaluation of durability and Water repellency of fiber product)

The water-repellent fiber product was washed 10 times (HL-10) by method 103 according to JIS L0217 (1995), and the water repellency after air drying was evaluated in the same manner as the above-mentioned water-repellent evaluation method.

[ Table 2]

The parts by mass of each component in table 2 are values in terms of solid content, and the comments and abbreviations in the table are as follows.

The weight ratio of the component (A) to the component (B) (in terms of solid content)

(abbreviation and details of Compound)

X-51-1302M: the solid content of the MQ resin emulsion manufactured by shin-Etsu chemical industries (ltd.) was 17%.

Claims

1. A water repellent composition comprising a dehydration condensate A of a 2-to 4-membered polycarboxylic acid a1 and a compound a2, wherein the compound a2 is at least 1 selected from an alcohol a 2-1 represented by the general formula (1) and an amine a 2-2 represented by the general formula (2),

R¹－OH···(1)

in the formula (1), R¹Represents an alkyl group or alkenyl group having 6 to 22 carbon atoms,

R²－NH－R³···(2)

in the formula (2), R²、R³Each independently represents a hydrogen atom, an alkyl group or alkenyl group having 6 to 22 carbon atoms, excluding R²And R³Both in the case of hydrogen atoms.

2. The water repellent composition according to claim 1, wherein the component a1 comprises at least 1 compound selected from the group consisting of citric acid, fumaric acid, malic acid, tartaric acid, succinic acid, and succinic anhydride.

3. The water repellent composition according to claim 1 or 2, wherein the component a2 comprises at least 1 selected from the group consisting of palmitol, stearyl alcohol, distearyl amine, dipalmityl amine, stearyl amine, palmityl amine and dihydrotallow amine.

4. A water repellent composition comprising the dehydration condensate A according to any one of claims 1 to 3 and a silicone B.

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

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

7. A water repellent fibrous article comprising a fiber and the water repellent composition of any one of claims 1 to 6 attached to the fiber.