Fiber structure

Abstract

A novel fiber structure exhibiting water repellency is provided by providing a fiber structure in which a water-repellent compound having a hydrocarbon group having 6-40 carbon atoms is attached to a fiber base material, the fiber structure having an air permeability of more than 20 cc / cm2 / sec. and a fabric density of more than 100 g / m2. A novel water repellent agent which can be used in the production of the fiber structure is also provided.

Description

Fiber structures

[0001] The present disclosure relates to textile structures, and more particularly to textile structures that have been treated with a water repellent treatment.

[0002] Patent Document 1 discloses a water repellent composition containing a polyurethane resin compound, a non-fluorine-containing water repellent compound, a surfactant, and a liquid medium. However, the publication does not specifically describe the breathability or fabric density of the substrate used. Furthermore, the publication does not consider the penetration resistance of the treated substrate (particularly, achieving both water repellency and penetration resistance).

[0003] International Publication No. 2021 / 132172

[0004] An object of the present disclosure is to provide a novel textile structure that exhibits water repellency, or a novel water repellent agent that can be used in producing such a textile structure.

[0005] The present disclosure includes the following aspects: [Item 1] A fiber structure having a water-repellent compound having a hydrocarbon group having 6 to 40 carbon atoms attached to a fiber substrate, the water-repellent compound having an air permeability of 20 cc / cm ２ / sec or more, and the fabric density is 100 g / m ２A fiber structure having a water-repellent property exceeding 100°C. [Item 2] The fiber structure according to Item 1, wherein the water-repellent compound is at least one selected from the group consisting of an acrylic polymer and an isocyanate derivative. [Item 3] The fiber structure according to Item 2, wherein the water-repellent compound comprises the acrylic polymer, and the acrylic polymer has a repeating unit derived from a multicarbonyl monomer having one ethylenically unsaturated double bond and two or more carbonyl groups. [Item 4] The fiber structure according to Item 2 or 3, wherein the water-repellent compound comprises the isocyanate derivative, and the isocyanate derivative has a moiety derived from a cationic active hydrogen compound. [Item 5] The fiber structure according to any one of Items 2 to 4, wherein the water-repellent compound comprises the acrylic polymer and the isocyanate derivative. [Item 6] The fiber structure according to any one of Items 2 to 5, wherein the water-repellent compound comprises the acrylic polymer and the isocyanate derivative, which has a water contact angle of 100° or more and has a moiety derived from a cationic active hydrogen compound. [Item 7] The fiber structure according to any one of Items 2 to 6, wherein the weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20. [Item 8] The fiber structure according to any one of Items 1 to 7, wherein the water repellency is Grade 4 or higher according to the spray test method specified in JIS L1092:2009, and the penetration rate according to the DIN 53924 test method is less than 10 mm / 2 h. [Item 9] The water-repellent compound comprises an acrylic polymer and an isocyanate derivative, wherein the acrylic polymer comprises a monomer (a) having a hydrocarbon group having from 6 to 40 carbon atoms, and wherein the monomer (a) is a monomer represented by the formula: CH2=C(-X ａ )-C(=O)-Y ａ (R ａ ) ｋ [In the formula, R ａ are each independently a hydrocarbon group having 6 to 40 carbon atoms; ａ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ[Item 10] A water repellent agent comprising a water-repellent compound having a hydrocarbon group having from 6 to 40 carbon atoms, wherein the water-repellent compound comprises an acrylic polymer and an isocyanate derivative, and the isocyanate derivative has a water contact angle of from 100° to 100° and has a moiety derived from a cationic active hydrogen compound, and the weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20. [Item 11] A water repellent agent comprising a water-repellent compound having a hydrocarbon group having from 6 to 40 carbon atoms, wherein the water-repellent compound comprises an acrylic polymer and an isocyanate derivative, and the isocyanate derivative has a water contact angle of from 100° to 100° and has a moiety derived from a cationic active hydrogen compound, and the weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20. [Item 11] The water repellent according to Item 10, wherein the acrylic polymer has a repeating unit derived from a multicarbonyl monomer having one ethylenically unsaturated double bond and two or more carbonyl groups. [Item 12] An air permeability of 20 cc / cm ２ / sec or more and fabric density 100g / m ２ [Item 13] A method for producing a fiber structure, comprising a step of treating a fiber substrate having a carbon number of 6 or more and a water repellent agent containing a water repellent compound having a hydrocarbon group having 6 to 40 carbon atoms. ２1. A method for producing a fiber structure, comprising treating a fiber substrate having a water repellent property of 6 to 40 carbon atoms with a water repellent agent, wherein the water repellent agent comprises a water repellent compound having a hydrocarbon group having 6 to 40 carbon atoms, the water repellent compound comprising an acrylic polymer and an isocyanate derivative, and the isocyanate derivative has a water contact angle of 100° or more and has a moiety derived from a cationic active hydrogen compound. [Item 14] The method for producing the fiber structure according to Item 13, wherein the weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20. [Item 15] The method for producing the fiber structure according to Item 13 or 14, wherein the water repellent compound comprises the acrylic polymer, and the acrylic polymer has a repeating unit derived from a multicarbonyl monomer having one ethylenically unsaturated double bond and two or more carbonyl groups.

[0006] According to the present disclosure, it is possible to provide a novel fiber structure that exhibits water repellency, or a novel water repellent agent that can be used in producing such a fiber structure.

[0007] <Definition of Terms> As used herein, an "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. Furthermore, an "n-valent organic group" refers to an n-valent group containing carbon. Such an organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A hydrocarbon group derivative refers to a group having one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the end or molecular chain of the hydrocarbon group.

[0008] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C １－２０Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents, if explicitly stated.

[0009] In this specification, when a term (symbol) that may appear multiple times in a chemical structure is defined, that definition applies independently at each occurrence, unless otherwise stated, regardless of whether "independently at each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated.

[0010] The chemical structures described herein should be understood not to encompass chemical structures that would be recognized by those skilled in the art as chemically impossible or extremely unstable.

[0011] <Water-Repellent Compound> The water-repellent compound in the present disclosure is capable of adhering to a substrate and imparting water repellency to the substrate, and may be a water-repellent compound having a hydrocarbon group having 6 to 40 carbon atoms.

[0012] [Characteristics, etc.] The water contact angle of the water-repellent compound may be 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, 100° or more, 105° or more, 110° or more, or 115° or more, preferably 100° or more, and may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the water-repellent compound has a water contact angle equal to or greater than the above lower limit, it can impart good water repellency to the substrate. The water contact angle is the static contact angle of the water-repellent compound with respect to a spin-coated film, and is obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle 1 second after the drop has landed.

[0013] The water-repellent compound in the present disclosure does not necessarily have any group selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the water-repellent compound does not contain these fluorine-containing groups, it can still impart liquid repellency to a substrate.

[0014] (Hydrocarbon Group Having 6 to 40 Carbon Atoms) The water-repellent compound may have a hydrocarbon group, particularly a hydrocarbon group having 6 to 40 carbon atoms. The hydrocarbon group having 6 to 40 carbon atoms contributes to imparting water repellency to the substrate.

[0015] The hydrocarbon group may be a monovalent hydrocarbon group. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched, cyclic, or linear, and is more preferably linear, particularly linear.

[0016] The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, or 16 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0017] Examples of the water-repellent compound are not particularly limited, but may be at least one selected from the group consisting of acrylic polymers and isocyanate derivatives, and a combination of an acrylic polymer and an isocyanate derivative is preferred. The amount of the acrylic polymer relative to the total of the acrylic polymer and the isocyanate derivative may be 10% by weight or more, 30% by weight or more, 50% by weight or more, 70% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 75% by weight or less, 55% by weight or less, 35% by weight or less, or 15% by weight or less. The weight ratio of the acrylic polymer to the isocyanate derivative is preferably 50 / 50 to 80 / 20. <Acrylic Polymer> In the present disclosure, an acrylic polymer may be used as the water-repellent compound. The acrylic polymer has a hydrocarbon group having from 6 to 40 carbon atoms.

[0018] The weight average molecular weight of the acrylic polymer may be 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; and may be 5,000,000 or less, 3,000,000 or less, 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, or 5,000 or less.

[0019] The water contact angle of the acrylic polymer may be 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, 100° or more, 105° or more, 110° or more, or 115° or more, and may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the acrylic polymer has a water contact angle equal to or greater than the above lower limit, it can impart good water repellency to the substrate. The water contact angle is the static contact angle of the acrylic polymer with a spin-coated film, and is obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle 1 second after the drop has landed.

[0020] (a) Hydrocarbon Group-Containing Monomer The acrylic polymer has repeating units derived from a monomer (a) having a hydrocarbon group having 6 to 40 carbon atoms.

[0021] The hydrocarbon group contained in the monomer (a) may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched or linear, and more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, 14 or more, or 16 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and preferably 30 or less, 25 or less, or 20 or less.

[0022] The monomer (a) may contain an amide group, a urea group, or a urethane group. The hydrocarbon-based monomer may be a combination of a hydrocarbon-based monomer having an amide group, a urea group, or a urethane group and a hydrocarbon-based monomer not having an amide group, a urea group, or a urethane group. When the monomer (a) contains such a group, the effects of the present disclosure can be effectively achieved.

[0023] The monomer (a) having a hydrocarbon group having 6 to 40 carbon atoms is represented by the formula: CH2=C(-X ａ )-C(=O)-Y ａ (R ａ ) ｋ [In the formula, R ａ are each independently a hydrocarbon group having 6 to 40 carbon atoms; ａ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ is a divalent to tetravalent group, and k is 1 to 3.

[0024] X ａ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. ａ Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. ａis preferably a hydrogen atom, a methyl group, or a chlorine atom. ａ is particularly preferably a hydrogen atom.

[0025] Y ａ is a divalent to tetravalent group. ａ is preferably a divalent group. ａ represents a hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ A group consisting of at least one selected from - and -NH- (excluding hydrocarbon groups) is preferred. Examples of hydrocarbon groups having one carbon atom include -CH ２ -, -CH(-) ２ or -C(-) ３ Examples include:

[0026] Y ａ -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, Y' is a direct bond, -O-, -NH- or -S(=O) ２ - and R' is -(CH ２ ) m - (m is an integer of 1 to 5) or -C ６ H ４ -(phenylene group).

[0027] Y ａ Specific examples of are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C ６ H ４ -, -O-(CH ２ ) m -O-, -NH-(CH ２ ) m -NH-, -O-(CH ２ ) m -NH-, -NH-(CH ２ )m -O-、-O-(CH ２ ) m -O-C(=O)-、-O-(CH ２ ) m -C(=O)-O-,-NH-(CH ２ ) m -O-C(=O)-,-NH-(CH ２ ) m -C(=O)-O-、-O-(CH ２ ) m -O-C(=O)-NH-,-O-(CH ２ ) m -NH-C(=O)-O-,-O-(CH ２ ) m -C(=O)-NH-,-O-(CH ２ ) m -NH-C(=O)-,-O-(CH ２ ) m -NH-C(=O)-NH-,-O-(CH ２ ) m -O-C ６ H ４ -、-O-(CH ２ ) m -NH-S(=O) ２ -、-O-(CH ２ ) m -S(=O) ２ -NH-、-NH-(CH ２ ) m -O-C(=O)-NH-,-NH-(CH ２ ) m -NH-C(=O)-O-,-NH-(CH ２ ) m -C(=O)-NH-,-NH-(CH ２ ) m -NH-C(=O)-,-NH-(CH ２ ) m -NH-C(=O)-NH-,-NH-(CH ２ ) m -O-C ６ H ４ -、-NH-(CH ２ ) m -NH-C ６ H ４ -、-NH-(CH ２ ) m-NH-S(=O) ２ -, or -NH-(CH ２ ) m -S(=O) ２ -NH-, wherein m is 1 to 5, particularly 2 or 4.

[0028] Y ａ is -O-, -NH-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -NH-S(=O) ２ -, -O-(CH ２ ) m -S(=O) ２ -NH-, -NH-(CH ２ ) m -NH-S(=O) ２ -, or -NH-(CH ２ ) m -S(=O) ２ -NH- [wherein m is an integer of 1 to 5, particularly 2 or 4] is preferred. ａ is -O- or -O-(CH ２ ) m —NH—C(═O)—, particularly —O—(CH ２ ) m It is more preferably —NH—C(═O)—.

[0029] R ａ is preferably a linear or branched hydrocarbon group. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22 carbon atoms.

[0030] Examples of the monomer (a) are: (a1) a monomer of the formula: CH2=C(-X ａ１ )-C(=O)-Y ａ１ -R ａ１ [In the formula, R ａ１ is a hydrocarbon group having 6 to 40 carbon atoms, ａ１ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ１ is —O— or —NH—.], and (a2) a monomer represented by the formula: CH═C(—X ａ２ )-C(=O)-Y ａ２１ -Z (-Y ａ２２ -R ａ２ ) ｎ [In the formula, R ａ２ are each independently a hydrocarbon group having 6 to 40 carbon atoms; ａ２ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ２１ is —O— or —NH—, and Y ａ２２ are each independently a direct bond, or —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２ -, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.

[0031] ((a1) Monomer) Monomer (a1) is a monomer represented by the formula: CH2=C(-X ａ１ )-C(=O)-Y ａ１ -R ａ１ [In the formula, R ａ１ is a hydrocarbon group having 6 to 40 carbon atoms, ａ１ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ１ is —O— or —NH—.]

[0032] The monomer (a1) is Y ａ１ a long chain acrylate ester monomer in which Y is —O—; ａ１ is a long chain acrylamide monomer in which is —NH—.

[0033] R ａ１ is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. ａ１ In the formula (I), the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 carbon atoms, and particularly preferably 18 to 22 carbon atoms.

[0034] X ａ１ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0035] Preferred examples of the long-chain acrylate ester monomer include lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, icosyl α-chloroacrylate, and behenyl α-chloroacrylate. Preferred examples of the long-chain acrylamide monomer include stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0036] (Monomer (a2)) The monomer (a2) is a monomer different from the monomer (a1). The monomer (a2) is a monomer selected from the group consisting of —O—, —C(═O)—, and —S(═O) ２ -, -NH- or -CH ２ The monomer (a2) is a (meth)acrylate or (meth)acrylamide having a group consisting of at least one selected from the formula: CH2=C(-X ａ２ )-C(=O)-Y ａ２１ -Z (-Y ａ２２ -R ａ２ ) ｎ [In the formula, R ａ２ are each independently a hydrocarbon group having 6 to 40 carbon atoms; ａ２ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ２１ is —O— or —NH—, and Y ａ２２ are each independently a direct bond, or —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2. ａ２２ and / or Z may not be a direct bond. ａ２２ and Z may not be a direct bond at the same time.

[0037] R ａ２ is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. ａ２ In the formula (I), the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22 carbon atoms.

[0038] X ａ２ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0039] Y ａ２２ represents -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'-, wherein each Y' independently represents a direct bond, -O-, -NH-, or -S(=O) ２ - and R' is -(CH ２ ) ｍ - (m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH ２ ) ｌ -C ６ H ４ -(CH ２ ) ｌ - (each l is independently an integer of 0 to 5; -C ６ H ４ - is a phenylene group.

[0040] Y ａ２２Specific examples thereof include direct bonding, -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O) ２ -, -S(=O) ２ -, -NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C ６ H ４ -, -NH-C ６ H ４ -, -O-(CH ２ ) m -O-, -NH-(CH ２ ) m -NH-, -O-(CH ２ ) m -NH-, -NH-(CH ２ ) m -O-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -C(=O)-O-, -NH-(CH ２ ) m -O-C(=O)-, -NH-(CH ２ ) m -C(=O)-O-, -O-(CH ２ ) m -O-C(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ )<从 m -C(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -O-C ６ H ４ -, -NH-(CH ２ ) m -O-C(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-O-, -NH-(CH ２ ) m -C(=O)-NH-, -NH-(CH ２ )m -NH-C(=O)-, -NH-(CH ２ ) m -NH-C(=O)-NH-, -NH-(CH ２ ) m -O-C ６ H ４ -, -NH-(CH ２ ) m -NH-C ６ H ４ wherein m is an integer of 1 to 5.

[0041] Y ａ２２ is -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O) ２ -, -S(=O) ２ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -OC ６ H ４ - is preferred. ａ２２ is more preferably —NH—C(═O)—, —C(═O)—NH—, —O—C(═O)—NH—, —NH—C(═O)—O— or —NH—C(═O)—NH—. ａ２２ may not be a direct bond.

[0042] Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a linear or branched structure. Z preferably has 2 to 4 carbon atoms, and particularly preferably 2. Specific examples of Z include a direct bond, -CH ２ -, -CH ２ CH ２ -, -CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ CH ２ -, -CH ２ CH(-) ２ , -CH ２ (CH-)CH２ -, -CH ２ CH ２ CH(-) ２ , -CH ２ CH ２ CH ２ CH ２ CH(-) ２ , -CH ２ CH ２ (CH-)CH ２ -, -CH ２ CH ２ CH ２ CH(-) ２ Z does not have to be a direct bond.

[0043] Monomer (a2) is CH2=C(-X ａ２ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R ａ２ , C.H. ２ =C(-X ａ２ )-C(=O)-O-(CH ２ ) ｍ -OC(=O)-NH-R ａ２ , C.H. ２ =C(-X ａ２ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-OR ａ２ , C.H. ２ =C(-X ａ２ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-NH-R ａ２ Preferably, R a２ and X ａ２ has the same meaning as above.]. The monomer (a2) is CH2=C(-X ａ２ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R ａ２ It is particularly preferred that:

[0044] Monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of long-chain alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate. Alternatively, monomer (a2) can be produced by reacting a (meth)acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0045] Preferred examples of the monomer (a) are as follows: stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, behenyl α-chloroacrylate; stearyl (meth)acrylamide, behenyl (meth)acrylamide;

[0046]

[0047]

[0048]

[0049]

[0050]

[0051] [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.] The compound of the above chemical formula is an acrylic compound having a hydrogen atom at the α-position, but specific examples may be a methacryl compound having a methyl group at the α-position and an α-chloroacrylic compound having a chlorine atom at the α-position.

[0052] The monomer (a2) has the formula:ａ２２ -C(=O)-NH-R ａ２３ -O-R ａ２１ [In the formula, R ａ２１ represents an organic residue having an ethylenically unsaturated polymerizable group, R ａ２２ represents a hydrocarbon group having 6 to 40 carbon atoms, R ａ２３ is a hydrocarbon group having 1 to 5 carbon atoms.]

[0053] R ａ２１ is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a carbon-carbon double bond. ａ２１１ =CH ２ , -CHR ａ２１１ =CH ２ , -CH ２ CHR ａ２１１ =CH ２ and the like. ａ２１１ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ａ２１ R may have various organic groups in addition to the ethylenically unsaturated polymerizable group, such as organic groups of chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents. ａ２１ is -C(=O)CR ａ２１１ =CH ２ It is preferable that:

[0054] R ａ２２ R is a hydrocarbon group having 6 to 40 carbon atoms, preferably an alkyl group, and examples thereof include chain hydrocarbon groups and cyclic hydrocarbon groups. Among these, a chain hydrocarbon group is preferred, and a linear saturated hydrocarbon group is particularly preferred. ａ２２ The number of carbon atoms is 6 or more and 40 or less, preferably 11 to 27, and particularly preferably 15 to 23.

[0055] R ａ２３ is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched, and may have an unsaturated bond, but is preferably linear. ａ２３The number of carbon atoms in R is preferably 2 to 4, and particularly preferably 2. ａ２３ is preferably an alkylene group.

[0056] The amide group-containing monomer is R ａ２２ is one type (for example, R ａ２２ is only a compound having 17 carbon atoms), or R ａ２２ A combination of multiple ａ２２ a compound having 17 carbon atoms, and R ａ２２ and a compound having 15 carbon atoms.

[0057] An example of the amide group-containing monomer is carboxylic acid amide alkyl (meth)acrylate.Specific examples of the amide group-containing monomer include palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth)acrylate, behenic acid amide ethyl (meth)acrylate, myristate amide ethyl (meth)acrylate, laurate amide ethyl (meth)acrylate, isostearate ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tertiary butylcyclohexyl caproate amide ethyl (meth)acrylate, adamantanecarboxylic acid ethyl amide (meth)acrylate, naphthalenecarboxylic acid amide ethyl (meth)acrylate, anthracenecarboxylic acid amide ethyl (meth)acrylate, palmitic acid amide propyl (meth)acrylate, stearic acid amide propyl (meth)acrylate, palmitic acid amide ethyl vinyl ether, stearic acid amide ethyl vinyl ether, palmitic acid amide ethyl allyl ether, stearic acid amide ethyl allyl ether, and mixtures thereof.

[0058] The amide group-containing monomer is preferably stearamidoethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamidoethyl (meth)acrylate. In the mixture containing stearamidoethyl (meth)acrylate, the amount of stearamidoethyl (meth)acrylate may be, for example, 40 wt% or more, 50 wt% or more, 60 wt% or more, or 70 wt% or more, and may be 90 wt% or less, 80 wt% or less, or 70 wt% or less, based on the total weight of the amide group-containing monomers. The remaining monomer may be, for example, palmitamidoethyl (meth)acrylate.

[0059] The amount of monomer (a2) in monomer (a) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, or 80% by weight or more, and is preferably 30% by weight or more.

[0060] [(b) Multicarbonyl Monomer] The acrylic polymer may have a repeating unit derived from a multicarbonyl monomer (b) having one ethylenically unsaturated double bond and two or more carbonyl groups.

[0061] The multicarbonyl monomer (b) is a compound represented by the following formula: CH2=C(-X ｂ１ )-C(=O)-Y ｂ１ -R ｂ１ -R ｂ２ [In the formula, X ｂ１ is a hydrogen atom, a monovalent organic group or a halogen atom, ｂ１ is —O— or —NH—, R ｂ１ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ｂ２ is a group having one or more carbonyl groups.

[0062] X ｂ１ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0063] Y ｂ１is —O— or —NH—, for example —O—.

[0064] R ｂ１ is a divalent hydrocarbon group having 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms). ｂ１ is preferably an aliphatic group. ｂ１ R may be a chain (linear or branched) or a cyclic group, and is preferably a chain, particularly a linear group. ｂ１ may be unsaturated or saturated, preferably saturated.

[0065] R ｂ１ is a divalent hydrocarbon group having 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms). ｂ１ is preferably an aliphatic group. ｂ１ R may be a chain (linear or branched) or a cyclic group, and is preferably a chain, particularly a linear group. ｂ１ may be unsaturated or saturated, preferably saturated.

[0066] R ｂ２ is a group having one or more carbonyl groups. ｂ２ The number of carbonyl groups contained in R may be 1 or more, 2 or more, or 3 or more, and is 4 or less, 3 or less, 2 or less, or 1, and preferably 1 or 2. ｂ２ The number of carbon atoms in R may be 1 to 20, and may be 1 or more, 3 or more, or 5 or more, and may be 20 or less, 15 or less, 10 or less, or 5 or less. ｂ２ Specific examples of the group include -CO-R ｂ２１ (where R ｂ２１ is a monovalent hydrocarbon group having 1 to 6 carbon atoms (for example, 1 to 4 or 1 to 2), a group represented by —NH—CO—NH2, or a 2-(2-oxo-1-imidazolidinyl) group.

[0067] Specific examples of the monomer (b) include diacetone acrylamide, 2-methylpropenoate [2-(2-oxo-2-imidazolidinyl)ethyl], N-[2-(2-oxoimidazolidin-3-yl)ethyl]methacrylamide, and 2-acetoacetoxyethyl (meth)acrylate. Among these, from the viewpoint of durable water repellency of textile products, diacetone acrylamide and 2-methylpropenoate [2-(2-oxo-2-imidazolidinyl)ethyl] are preferred as the component (A2).

[0068] [(c) Halogenated Olefin Monomer] The acrylic polymer may have a repeating unit derived from a halogenated olefin monomer (c). The halogenated olefin monomer (c) may not contain fluorine atoms. The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms and substituted with 1 to 10 chlorine, bromine, or iodine atoms. The halogenated olefin monomer (c) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and 1 to 5 chlorine atoms. Preferred examples of the halogenated olefin monomer include vinyl halides, such as vinyl chloride, vinyl bromide, and vinyl iodide, and vinylidene halides, such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred because it enhances water repellency (particularly water repellency durability). The presence of repeating units derived from the halogenated olefin monomer (c) can enhance the washing durability provided by the water-repellent compound.

[0069] [(d) Crosslinkable Monomer] In the acrylic polymer, the crosslinkable monomer (d) has at least two reactive groups and / or ethylenically unsaturated double bonds (preferably, (meth)acrylate groups), and the crosslinkable monomer (e) may be a monomer that does not contain fluorine atoms. It may also be a compound that does not contain fluorine atoms. The crosslinkable monomer (d) may be a compound that has at least two ethylenically unsaturated double bonds (preferably, (meth)acrylate groups), or a compound that has at least one ethylenically unsaturated double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, and a carboxyl group.

[0070] The crosslinkable monomer (d) may be a mono(meth)acrylate, di(meth)acrylate or di(meth)acrylamide having a reactive group.

[0071] An example of the crosslinkable monomer (d) is a vinyl monomer having a reactive group.

[0072] Examples of the crosslinkable monomer (d) include, but are not limited to, 3-chloro-2-hydroxypropyl(meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0073] [(e) Cyclic Hydrocarbon Group-Containing Monomer] The acrylic polymer may contain a cyclic hydrocarbon group-containing monomer (e). The cyclic hydrocarbon group-containing monomer (e) is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.

[0074] The cyclic hydrocarbon group-containing monomer (e) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0075] The cyclic hydrocarbon group may be alicyclic or aromatic, preferably alicyclic. The cyclic hydrocarbon group may be saturated or unsaturated, preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, preferably a bridged ring group. The cyclic hydrocarbon group may have a chain group (e.g., a linear or branched chain hydrocarbon group).

[0076] The cyclic hydrocarbon group may have 4 or more, 6 or more, or 8 or more carbon atoms, and may have 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less carbon atoms.

[0077] Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butylcyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a bornyl group, an isobornyl group, a norbornyl group, a dicyclopentanyl group, a dicyclopentenyl group, a benzyl group, a phenyl group, a naphthyl group, a 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (for example, a cyclohexylene group, an adamantylene group, a phenylene group, a naphthylene group, etc.), and groups which are substitution products thereof.

[0078] Specific examples of the cyclic hydrocarbon group-containing monomer (e) include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and compounds in which these acrylates are substituted with acrylamide, etc. These may be used alone or in combination of two or more.

[0079] [(f) Hydrophilic Group-Containing Monomer] The acrylic polymer may contain a hydrophilic group-containing monomer (f). The monomer (f) is a monomer having a hydrophilic group. The hydrophilic group is preferably an oxyalkylene group (the alkylene group has 2 to 6 carbon atoms), particularly an oxyethylene group. In particular, the monomer (f) is preferably an oxyalkylene (meth)acrylate, for example, polyalkylene (or monoalkylene) glycol mono(meth)acrylate and / or polyalkylene (or monoalkylene) glycol di(meth)acrylate, or polyalkylene (or monoalkylene) glycol mono(meth)acrylamide.

[0080] The monomer (f) has the formula: CH ２ =CX ｆ C(=O)-Y ｆ - (R ｆ O) ｎ -A ｆ [In the formula, X ｆ is a hydrogen atom or a methyl group, and Y ｆ is —O— or —NH—, R ｆ are each independently an alkylene group having 2 to 6 carbon atoms, ｆ represents a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH ２ =CX ｆ C(═O)—, and n is an integer of 1 to 90.

[0081] Examples of monomers (f) are those of the formula: ２ =CX ｆ C(=O)-O-(R ｆ O) ｎ -A ｆｉ (f1) CH ２ =CX ｆ C(=O)-O-(R ｆ O) ｎ -C(=O)CX ｆ =CH ２ (f2), CH ２ =CX ｆ C(=O)-NH-(R ｆ O) ｎ -Aｆｉ (f3) [wherein, X ｆ are each independently a hydrogen atom or a methyl group; ｆｉ are each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, ｆ are each independently an alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 to 90.

[0082] n may be, for example, 1 or more, 2 or more, or 3 or more, and may be 50 or less, 30 or less, or 15 or less. Alternatively, n may be, for example, 1. ｆ may be a linear or branched alkylene group, for example, a group of the formula -(CH ２ ) ｘ - or - (CH ２ ) ｘ１ -(CH(CH ３ )) ｘ２ - [wherein x1 and x2 are 0 to 6, for example, 2 to 5, and the sum of x1 and x2 is 1 to 6. -(CH ２ ) ｘ１ - and - (CH (CH ３ )) ｘ２ The order of - is not limited to the illustrated formula and may be random. ｆ O) n In -, R may be two or more types (for example, two to four types, particularly two types), and -(R ｆ O) n - is, for example, -(R １ O) ｎ１ - and - (R ２ O) ｎ２ - [wherein, R １ and R ２ are different from each other and are alkylene groups having 2 to 6 carbon atoms, n1 and n2 are numbers of 1 or more, and the sum of n1 and n2 is 2 to 90.

[0083] R in formulas (f1), (f2) and (f3) ｆ is particularly preferably an ethylene group, a propylene group or a butylene group, and particularly preferably a butylene group.ｆ R may be a combination of two or more alkylene groups. In this case, it is preferable that at least one of R is an ethylene group, a propylene group, or a butylene group. ｆ Examples of the combination include a combination of an ethylene group / propylene group, a combination of an ethylene group / butylene group, and a combination of a propylene group / butylene group. The monomer (f) may be a mixture of two or more types. In this case, at least one of the monomers (f) is a mixture of R in formula (f1), (f2), or (f3). ｆ is preferably an ethylene group, a propylene group, or a butylene group. When a polyalkylene glycol di(meth)acrylate represented by formula (f2) is used, it is not preferable to use it alone as the monomer (f), but it is preferable to use it in combination with the monomer (f1). In that case, it is also preferable to keep the content of the compound represented by formula (f2) to less than 30% by weight of the monomer (f) used.

[0084] The monomer (f) may be X ２ is a hydrogen atom. The monomer (f) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

[0085] [(g) Ion-donating group-containing monomer] The acrylic polymer may contain an ion-donating group-containing monomer (g). The monomer (g) is preferably a monomer (particularly an acrylic monomer) containing an olefinic carbon-carbon double bond and an ion-donating group. The ion-donating group is an anion-donating group and / or a cation-donating group.

[0086] Examples of the monomer having an anion donating group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Specific examples of the monomer having an anion donating group include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylate phosphate, vinylbenzenesulfonic acid, acrylamido-tertiarybutylsulfonic acid, and salts thereof.

[0087] Salts of anion-donating groups include alkali metal salts, alkaline earth metal salts, and ammonium salts such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0088] In the monomer having a cation donating group, examples of the cation donating group are amino groups, preferably tertiary amino groups and quaternary amino groups. In the tertiary amino group, two groups bonded to the nitrogen atom may be the same or different and may be an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an aromatic aliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cation donating group may be in the form of a salt.

[0089] The cation-donating group in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid), are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and salts thereof are preferred.

[0090] The ion-donating group-containing monomer (c) is preferably methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate, and more preferably methacrylic acid or dimethylaminoethyl methacrylate.

[0091] [(h) Other Monomers] The other monomers are not limited to these examples, but include acrylonitrile, organosiloxane-containing (meth)acrylates, short-chain alkyl (meth)acrylates, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, vinyl alkyl ethers, etc. The other monomers (h) may be used alone or in combination of two or more.

[0092] [Polymer Composition] The combination of monomers (a) to (h) constituting the repeating units of the acrylic polymer is not particularly limited. The acrylic polymer preferably contains, in addition to the repeating units derived from monomer (a), repeating units derived from monomer (b) and / or repeating units derived from monomer (c). In the case of textile products, it is preferable to use the monomers (a), (d), (e), and (g) in combination.

[0093] The amount of repeating units derived from monomer (a) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, preferably 25% by weight or more, more preferably 50% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the acrylic polymer.

[0094] The amount of repeating units derived from monomer (b) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the acrylic polymer. The amount of the repeating units derived from monomer (b) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0095] The amount of repeating units derived from monomer (c) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the acrylic polymer. The amount of the repeating units derived from monomer (c) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0096] The amount of repeating units derived from monomer (d) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the acrylic polymer. The amount of the repeating units derived from monomer (d) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0097] The amount of repeating units derived from monomer (e) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the acrylic polymer. The amount of the repeating units derived from monomer (e) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0098] The amount of repeating units derived from monomer (f) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the acrylic polymer. The amount of the repeating units derived from monomer (f) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0099] The amount of repeating units derived from monomer (g) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the acrylic polymer. The amount of the repeating units derived from monomer (g) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a).

[0100] The amount of repeating units derived from monomer (h) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the acrylic polymer. The amount of the repeating units derived from monomer (h) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0101] [Polymerization Method] The acrylic polymer can be produced by a known polymerization method, and the polymerization reaction conditions can be selected arbitrarily. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0102] In solution polymerization, a method is employed in which monomers are dissolved in an organic solvent in the presence of a polymerization initiator, and after purging with nitrogen, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of the monomers.

[0103] The organic solvent is inert to the monomers and dissolves them, and may be, for example, an ester (e.g., an ester having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 3,000 parts by weight, for example, 50 to 2,000 parts by weight, per 100 parts by weight of the total of the monomers.

[0104] Emulsion polymerization involves emulsifying monomers in water in the presence of a polymerization initiator and an emulsifier, purging with nitrogen, and then polymerizing the mixture at a temperature ranging from 50 to 80°C for 1 to 20 hours with stirring. Examples of polymerization initiators that can be used include water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount ranging from 0.01 to 10 parts by weight per 100 parts by weight of the monomer.

[0105] To obtain a polymer aqueous dispersion with excellent shelf stability, it is desirable to polymerize the monomer by microparticulating it in water using an emulsifying device capable of applying powerful crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and are used in a range of 0.5 to 20 parts by weight per 100 parts by weight of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely compatible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent or a low-molecular-weight monomer, that will fully compatibilize these monomers. Addition of a compatibilizer can improve emulsification and copolymerization properties.

[0106] The water-soluble organic solvent may be any of the organic solvents described above. Examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. Examples of low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0107] A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomers.

[0108] <Isocyanate Derivative> In the present disclosure, an isocyanate derivative may be used as the water-repellent compound. The isocyanate derivative has a hydrocarbon group having 6 to 40 carbon atoms.

[0109] The isocyanate derivative is a compound obtained by reacting an active hydrogen compound with a raw material isocyanate, and has a portion derived from the active hydrogen-containing compound and a portion derived from the raw material isocyanate. Unlike isocyanate-based curing agents, the isocyanate derivative does not usually have an isocyanate group.

[0110] The isocyanate derivative has an -NHCO- group formed by the reaction of an active hydrogen compound with a raw material isocyanate (wherein -NHCO- may be part of a urethane group or a urea group). -NHCO- is a group formed by the reaction of an active hydrogen-containing group (typically a hydroxy group) of the active hydrogen compound with an active hydrogen-reactive group (typically an isocyanate group) of the raw material isocyanate. The isocyanate derivative is typically a urethane (particularly a polyurethane).

[0111] The hydrocarbon group of the isocyanate derivative having 6 to 40 carbon atoms may be a monovalent hydrocarbon group. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched, cyclic, or linear, and is more preferably linear, particularly linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, or 16 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and preferably 30 or less, 25 or less, or 20 or less.

[0112] The weight average molecular weight of the isocyanate derivative may be 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, or 5,000 or less.

[0113] The water contact angle of the isocyanate derivative may be 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, 100° or more, 105° or more, 110° or more, or 115° or more, and may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the isocyanate derivative has a water contact angle equal to or greater than the above lower limit, it can impart good water repellency to the substrate. The water contact angle is the static contact angle of the isocyanate derivative with respect to a spin-coated film, and is obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle 1 second after the drop lands.

[0114] [Active Hydrogen Compound] The active hydrogen compound contains an active hydrogen group that reacts with an isocyanate group.

[0115] Examples of the active hydrogen group include a hydroxy group, an amino group, and a carboxyl group, and a typical example is a hydroxy group.

[0116] [(α1) Hydrocarbon Alcohol] The active hydrogen compound may be an active hydrogen compound (α1) composed of a hydrocarbon group and a hydroxyl group.

[0117] The hydrocarbon group in the active hydrogen compound (α1) is the aforementioned hydrocarbon group having 6 to 40 carbon atoms, and the above description is incorporated herein.

[0118] The active hydrogen compound (α1) preferably has one hydroxy group per molecule.

[0119] Examples of the active hydrogen compound (α1) include linear saturated hydrocarbon group-containing alcohols such as n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol, and eicosanol; branched saturated hydrocarbon group-containing alcohols such as isomyristyl alcohol, isocetyl alcohol, isostearyl alcohol, and isoicosyl alcohol; linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, icosenyl alcohol, docosenyl alcohol, tetracosenyl alcohol, hexacosenyl alcohol, and octacosenyl alcohol; and branched unsaturated hydrocarbon group-containing active hydrogen compounds such as phytol.

[0120] Here, a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol may be used in combination, and when a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol are used in combination, the blending ratio of the linear saturated hydrocarbon group-containing alcohol is, for example, 40 parts by mass or more, preferably 55 parts by mass or more, more preferably 70 parts by mass or more, and for example, 90 parts by mass or less, preferably 80 parts by mass or less, per 100 parts by mass of the total of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. The blending ratio of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, and for example, 60 parts by mass or less, preferably 45 parts by mass or less, more preferably 30 parts by mass or less, per 100 parts by mass of the total of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. When the blending ratio of the linear saturated hydrocarbon group-containing alcohol is equal to or greater than the above lower limit, the crystallinity of the hydrocarbon group is improved, and as a result, the water repellency of the water-repellent treated object treated with this water repellent composition can be improved.

[0121] [(α2) Sugar alcohol / hydroxy acid modified compound] The active hydrogen compound may be a sugar alcohol / hydroxy acid modified compound (α2), which is a sugar alcohol / hydroxy acid (sugar alcohol and / or hydroxy acid) in which a hydrocarbon group having from 6 to 40 carbon atoms has been modified. The type of sugar alcohol / hydroxy acid is not limited and may be cyclic or acyclic. Examples of sugar alcohols include monosaccharides, reducing sugars, amino sugars, aldonic acids, and aldonic acid lactones, and examples of hydroxy acids include hydroxy polycarboxylic acids. The sugar alcohol / hydroxy acid may be a substance present in a living body. Examples of sugar alcohols / hydroxy acids include, but are not limited to, compounds derived from aldoses and ketoses, such as tetroses, pentoses, hexoses, and heptoses, and specific examples include glucose, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, gulose, galactose, talose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol, threitol, glucopyranose, mannopyranose, and the like. Examples of suitable sugar alcohols / hydroxy acids include talopyranose, allopyranose, altropyranose, idopyranose, gulopyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fucitol, iditol, inositol, pentaerythritol, dipentaerythritol, volemitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, citric acid, gluconic acid lactone, glyceric acid lactone, xylonic acid lactone, glucosamine, galactosamine, and mixtures thereof. The number of carbon atoms in the sugar alcohol / hydroxy acid may be 2 or more, 4 or more, or 6 or more, and may be 30 or less, 20 or less, or 10 or less. The average OH value of compound (α2) may range from greater than 0 to about 230, preferably from about 10 to about 175, and most preferably from about 25 to about 140.

[0122] The number of hydrocarbon groups having from 6 to 40 carbon atoms in the sugar alcohol / hydroxy acid modified product (α2) may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more. The number of hydrocarbon groups having from 6 to 40 carbon atoms in the sugar alcohol / hydroxy acid modified product (α2) may be 12 or less, 9 or less, 6 or less, or 3 or less.

[0123] In the sugar alcohol / hydroxy acid modified compound (α2), at least one active hydrogen atom (for example, a hydrogen atom in an OH group or a carboxyl group) of the sugar alcohol and / or the hydroxy acid is -R α２ , -C(O)R α２ , -(CH2CH2O) n (CH(CH3)CH2O) m R α２ , -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α２ or mixtures thereof, wherein R α２ is a hydrogen atom or a hydrocarbon group having from 6 to 40 carbon atoms, each n is independently 0 to 20, each m is independently 0 to 20, and m+n may be greater than 0. Compound (α2) has at least one active hydrogen, and for example, in a sugar alcohol / hydroxy acid modified product, at least one (one or more) of the active hydrogens of the sugar alcohol / hydroxy acid may be unmodified, and the active hydrogen (e.g., an —OH group) may react with an active hydrogen reactive group (particularly an isocyanate group) of compound (b) to form —NHCO—.

[0124] ((α21) Sorbitan Modification) The sugar alcohol / hydroxy acid modification (α2) may be a sorbitan modification (α21) in which sorbitan is modified with a hydrocarbon group having 6 to 40 carbon atoms, and may be, in particular, an alkylsorbitan, and the sorbitan may be modified with -R α２ , -C(O)R α２ , -(CH2CH2O) n (CH(CH3)CH2O) m R α２ , -(CH2CH2O) n (CH(CH3)CH2O) m C(O)Rα２ or a mixture thereof (wherein R α２ is a hydrocarbon group having 6 to 40 carbon atoms). For example, sorbitan can be converted to -C(O)R α２ The alkyl sorbitan may be a mono-, di-, or tri-substituted compound. Here, the sorbitan may contain an amount of sorbitol, isosorbide, or other intermediates or by-products. Commercially available sorbitans such as SPAN can be used as the alkyl sorbitan.

[0125] In one embodiment, at least one active hydrogen substituent is —C(O)R α２ and R α２ may be a straight or branched chain alkyl group having 6 to 40 carbon atoms, more preferably 7 to 21 carbon atoms, and most preferably 11 to 21 carbon atoms. Preferred compounds include mono-, di-, and tri-substituted sorbitans derived from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and mixtures thereof. Particularly preferred compounds include mono-, di-, and tri-substituted sorbitan stearates or sorbitan behenin.

[0126] In one embodiment, R α２ may contain at least one unsaturated bond. Examples of such compounds (wherein at least one active hydrogen substituent is —C(O)R α２ and R α２ contains at least one unsaturated bond), sorbitan trioleate (i.e., in which R α２ Ha-C7H 14 CH=CHC8H 17 Other examples include, but are not limited to, mono-, di-, and tri-substituted sorbitans derived from palmitoleic acid, linoleic acid, arachidonic acid, and erucic acid.

[0127] In one embodiment, the sorbitan modification (α21) has at least one active hydrogen substituent, and the active hydrogen substituent is independently —(CHCHO). n (CH(CH3)CH2O)m R α２ or -(CHCHO) n (CH(CH3)CH2O) m C(O)R α２ (wherein each m is independently 0 to 20, each n is independently 0 to 20, and m+n is greater than 0.) Such compounds are known as polysorbates and are commercially available under the trade name TWEEN. These sorbitans are also known as R α２ Commercially available polysorbates can be mono-, di-, or trisubstituted with each R 2 From various polysorbates where R is H (unsubstituted), α２ It is known that sorbitan derivatives contain a wide variety of mixtures ranging from polysorbates in which m is a linear or branched alkyl group having 6 to 40 carbons (fully substituted), and mixtures of these various substitutions. Examples of such sorbitan modifications (α21) include polysorbates such as polysorbate tristearate and polysorbate monostearate. m+n is greater than 0 and R α２ Examples of sorbitan modifications (α21) containing at least one unsaturated bond include, but are not limited to, polysorbate trioleate (where R α２ is C7H 14 CH=CHC8H 17 and is commercially available under the name Polysorbate 80. Sorbitan modifications (α21) may include mixtures of compounds with various active hydrogen substituents, and R α２ a compound in which R α２ may include mixtures with fully saturated compounds.

[0128] ((α22) Citric Acid Modification) The sugar alcohol / hydroxy acid modification (α2) may be a citric acid modification (α22) in which citric acid is modified with a hydrocarbon group having from 6 to 40 carbon atoms, and may in particular be an alkyl citrate. For example, the citric acid modification (α22) may exist as a mono-, di-, or tri-substituted product with alkyl groups. Mixtures of citrates with various values ​​of active hydrogen substituents may also be used, and Rα２ a compound having a hydrocarbon group having at least one unsaturated bond, and R α２ The citric acid modification (α22) may contain a mixture of -(CH2CH2O) and a compound in which -(CH2CH2O) is a fully saturated hydrocarbon. n (CH(CH3)CH2O) m R α２ or -(CHCHO) n (CH(CH3)CH2O) m C(O)R α２ wherein R α２ is a hydrocarbon group having 6 to 40 carbon atoms.) Examples of citric acid modifications (α22) include, but are not limited to, trialkyl citrates.

[0129] ((α23) Pentaerythritol Modification) The sugar alcohol / hydroxy acid modification (α21) may be a pentaerythritol modification (α23) in which pentaerythritol is modified with a hydrocarbon group having from 6 to 40 carbon atoms, and may be a mono-, di-, or tri-substituted product having a hydrocarbon group (particularly an alkyl group) having from 6 to 40 carbon atoms, such as a dipentaerythriol ester. The active hydrogen substituent is —CHC[CHOR α２ ]3, where R α２ is a hydrocarbon group having 6 to 40 carbon atoms.) The pentaerythritol modification (α23) is a compound having a mixture of hydrocarbon groups with different chain lengths, or R α２ a compound in which R α２ The carboxylic acid may contain a mixture of fully saturated compounds with the carboxylic acid.

[0130] [(α3) Cationic Active Hydrogen Compound] The active hydrogen compound may be a cationic active hydrogen compound (α3) having an active hydrogen group and a cationic group.

[0131] The cationic active hydrogen compound (α3) preferably has two or more hydroxy groups per molecule.

[0132] An example of the cationic group is a tertiary amino group.

[0133] That is, the cationic active hydrogen compound (α3) preferably has two or more hydroxyl groups per molecule as active hydrogen groups and a tertiary amino group as a cationic group.

[0134] Such cationic active hydrogen compounds can impart good dispersibility in a liquid medium (e.g., water) and can also introduce cationic groups having affinity for textile products (described later) into the resin, thereby improving washing durability.

[0135] More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as the active hydrogen groups and a tertiary amino group as the cationic group.

[0136] Examples of such cationic active hydrogen compounds include alkyldialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, and propanolamine, and trialkanolamines such as N-triethanolamine and N-triisopropanolamine, and preferably N-methyldiethanolamine.

[0137] The cationic active hydrogen compound (or the portion of the water-repellent compound derived from the cationic active hydrogen compound) may form a salt with an acid compound.

[0138] Examples of the acid compound include organic acids and inorganic acids. Examples of the organic acid include acetic acid, lactic acid, tartaric acid, malic acid, etc., preferably acetic acid and lactic acid, more preferably acetic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, etc., preferably hydrochloric acid. Examples of the acid compound include organic acids. When the acid compound contains an organic acid, the acid volatilizes upon heat treatment, thereby improving the water repellency of the water-repellent treated material treated with this water repellent composition. Furthermore, the acid volatilizes upon heat treatment, which makes it easier for cationic groups to adsorb to textile products, thereby improving the washing durability of the textile products. [(α4) Other active hydrogen-containing compounds] The active hydrogen compound may contain other active hydrogen compounds (α4).

[0139] ((α41) Compound) The active hydrogen compound (α4) is represented by the formula R α４１ -X α４１ [In the formula, In the formula, R α４１ is a C1-C2 alkyl group which may contain at least one unsaturated group; 30 Straight or branched chain alkyl, hydroxy-functional C1-C 30 Straight or branched chain alkyl, hydroxy-functional straight or branched chain C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy-functional linear or branched organosiloxanes, thiol-functional C1-C 30 Straight or branched alkyl, amine functional C1-C 30 linear or branched alkyl, Y － R α４１１ R α４１２ R α４１３ N ＋ -R α４１４ - (where Y is a halide ion, e.g., Cl － ), HOS(=O) ２ -R α４１４ - or R α４１１ R α４１２ C=N- (where R α４１１ , R α４１２ , R α４１３ are each independently —H or C1-C6 alkyl, and R α４１４is a divalent alkyl group having 1 to 20 carbon atoms; α４１ is -OH, -C(O)OH, -SH, -NH(R'), -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CHCHO) s (CH(CH3)CH2O) t isocyanate-reactive functional groups such as —H, where R ’ represents —H or a monovalent organic group, s represents an integer of 0 to 50, t represents an integer of 0 to 50, and s+t is greater than 0.

[0140] Compound (α41) may be a hydrophilic, water-soluble material comprising at least one hydroxy-terminated polyether, wherein X α４１ is -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CH2CH2O)s(CH(CH3)CH2O) t The -(CHCHO)- represents an oxyethylene group (EO), and the -(CH(CH)CHO)- represents an oxypropylene group (PO). These polyethers can contain only EO groups, only PO groups, or a mixture thereof. These polyethers may also exist as designated PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol) triblock copolymers.

[0141] In one embodiment, X α４１ is -OH, -C(O)OH, -SH, -NH(R ’ ) and R α４１ is a C-C group optionally containing at least one unsaturated group 30 Straight or branched chain alkyl, hydroxy-functional C1-C 30 Straight or branched chain alkyl, hydroxy-functional straight or branched chain C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy- or amine-functional linear or branched organosiloxanes, thiol-functional C1-C30 Straight or branched alkyl, amine functional C1-C 30 It is selected from straight or branched chain alkyl.

[0142] X α４１ may be —OH, and examples of such compounds (α41) include alkyl alcohols such as propanol, butanol, or fatty alcohols including stearyl alcohol (R α４１ optionally containing at least one unsaturated group, C1-C 30 alkyl diols or polyols (R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R α４１ is a hydroxy-functional C-C 30 alkylene glycol ethers such as triethylene glycol, tetraethylene glycol, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), or glycol ethers (R ) having a mixture of PEG, PPG or THF units; α４１ is a hydroxy-functional straight or branched chain C-C 30 Polyether), polyester polyol (R α４１ is a hydroxy-functional linear or branched polyester), silicone prepolymer polyol (R α４１ is a hydroxy-functional linear or branched organosiloxane), N,N-dimethylaminoethanol (R α４１ is an amine functional C-C 30 straight or branched chain alkyl), choline chloride or betaine HCl (R α４１ Is Y － R α４１１ R α４１２ R α４１３ N ＋ -R α４１４ -), butanone oxime (R α４１ is R α４１１ R α４１２Polyether polyols include, but are not limited to, polyether glycols (wherein the hydroxyl group is C═N—). The polyether polyols can contain only EO groups, only PO groups, only THF groups, or mixtures thereof. These polyethers can also exist as block copolymers, such as those designated by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). The polyether glycols preferably have an average molecular weight of about 200 or greater, most preferably 350 to 2000.

[0143] X α４１ may be —C(O)OH, and examples of such compounds (α41) include fatty acids (R α41) such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, linoleic acid, arachidonic acid, oleic acid, or erucic acid. α４１ is a C-C group optionally containing at least one unsaturated group 30 hydroxy-containing acids (R alkyl esters), such as hydroxycaprylic acid, hydroxycapric acid, hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyarachidic acid, hydroxybehenic acid, hydroxylignoceric acid, hydroxypalmitoleic acid, hydroxylinoleic acid, hydroxyarachidonic acid, hydroxyoleic acid, or hydroxyerucic acid; α４１ is a hydroxy-functional C-C 30 linear or branched alkyl), and mercaptoalkanoic acids such as mercaptopropionic acid (R α４１ is a thiol functional C-C 30 and the like. The alkyl groups include, but are not limited to, straight or branched chain alkyl groups.

[0144] X α４１ may be —SH, and examples of such compounds (α41) include alkyl thiols (R α４１ is a C-C group optionally containing at least one unsaturated group 30and the like. The alkyl groups include, but are not limited to, straight or branched chain alkyl groups.

[0145] X α４１ may be —NH(R′), and examples of such compounds (α41) include alkylamines (R α４１ is a C-C group optionally containing at least one unsaturated group 30 an alkanolamine (R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 2 α４１ is a hydroxy-functional C-C 30 linear or branched alkyl), silicone prepolymer polyamine (R α４１ is an amine-functional linear or branched organosiloxane), alkyldiamine (R α４１ is an amine functional C-C 30 straight-chain or branched-chain alkyl), and aminoalkanesulfonic acids such as 2-aminoethanesulfonic acid (R α４１ is HO-S(O)2R α４１４ -), but are not limited to.

[0146] (Compound (α42)) Compound (α42) is a compound represented by the formula R α４２１ -(OCH2CH(OR α４２２ ) CH2) z -OR α４２３ [In the formula, R α４２１ , R α４２２ and R α４２３ is at least one R α４２１ , R α４２２ or R α４２３ are —H, and each independently represents —H, —R α４２４ , -C(O)R α４２４ and R α４２４ are independently a straight-chain or branched-chain alkyl group having 5 to 29 carbon atoms which may contain at least one unsaturated bond, and z is 1 to 15.

[0147] Compound (α42) may be a compound generally known as polyglycerol. Other specific examples include, but are not limited to, triglycerol monostearate, triglycerol distearate, hexaglycerol monostearate, hexaglycerol distearate, decaglyceryl mono(caprylate / caprate), decaglyceryl di(caprylate / caprate), decaglycerol, polyglycerol-3, and C18 diglyceride.

[0148] ((α43) Chain extender) The compound (α4) may be a chain extender (α43). The chain extender (α43) is a compound having two or more (for example, two) functional groups containing active hydrogen in the molecule. As the chain extender, known chain extenders can be used, and examples thereof include aliphatic or aromatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanedimethanol; aliphatic or aromatic diamines or polyamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, and diethyltoluenediamine; phenolic hydroxyl group-containing compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol, and o,o'-diallyl-bisphenol A; and alcohol amines such as aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine, aminopropylpropanolamine, and aminohexylpropanolamine.

[0149] Starting Isocyanate The water repellent compound has a moiety derived from the starting isocyanate.

[0150] Examples of raw material isocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4', or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethyl xylylene diisocyanate (1,3- or aromatic polyisocyanates selected from 1,4-tetramethylxylylene diisocyanate or mixtures thereof (TMXDI), ω,ω'-diisocyanato-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4-, or 1,8-naphthalene diisocyanate or mixtures thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate;acyclic aliphatic polyisocyanates selected from trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaprate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate; 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylenebis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate or a mixture thereof) (hydrogenated MDI), methylcyclohexyl Cycloalicyclic polyisocyanates selected from among methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), and hydrogenated tetramethylxylylene diisocyanate (hydrated TMXDI); bridged cycloaliphatic polyisocyanates selected from among norbornene diisocyanate, norbornane diisocyanatomethyl, bicycloheptane triisocyanate, diisocyanatomethyl bicycloheptane, and di(diisocyanatomethyl)tricyclodecane; and biuret-modified products of the above-mentioned isocyanates, polymers of polyisocyanates (for example, dimers, trimers (for example, isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), allophanate derivatives (for example, allophanate derivatives produced by the reaction of the above-mentioned polyisocyanates with monohydric alcohols or dihydric alcohols), polyol derivatives (for example, polyol derivatives (alcohol adducts, preferably trimethylolpropane) produced by the reaction of the above-mentioned polyisocyanates with trihydric alcohols (for example, trimethylolpropane, etc.) Examples of the derivatives include biuret derivatives (e.g., biuret derivatives formed by the reaction of the above-mentioned polyisocyanates with water or amines), urea derivatives (e.g., urea derivatives formed by the reaction of the above-mentioned polyisocyanates with diamines), oxadiazinetrione derivatives (e.g., oxadiazinetrione formed by the reaction of the above-mentioned polyisocyanates with carbon dioxide), carbodiimide derivatives (e.g., carbodiimide derivatives formed by the decarboxylation condensation reaction of the above-mentioned polyisocyanates), uretdione derivatives, and uretonimine derivatives.

[0151] The average number of isocyanate groups in the raw material isocyanate is 2 or more, preferably 2.5, more preferably 2.9, and for example, 3.8 or less. The raw material isocyanate may be a polyisocyanate having a plurality of isocyanate groups.

[0152] [Method for synthesizing isocyanate derivatives]

[0153] To obtain an isocyanate derivative, an active hydrogen compound is reacted with a raw material isocyanate. The reaction may be carried out in one step or in multiple successive steps. For example, if unreacted active hydrogen groups or active hydrogen-reactive groups exist in the product, the synthesis may be carried out successively. Successive reactions are particularly useful when using a substituted sugar alcohol with a high OH number. Reaction conditions such as reaction concentration and reaction temperature are not particularly limited and can be determined by those skilled in the art. Specifically, the active hydrogen compound and raw material isocyanate may be blended so that the equivalent ratio of active hydrogen-reactive groups (isocyanate groups) to active hydrogen groups (active hydrogen-reactive groups / active hydrogen groups) is, for example, 1.2 or more, preferably 1.5 or more, and, for example, 2.0 or less.

[0154] [Composition of Water-Repellent Compound] The amount of the portion derived from the active hydrogen compound may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, based on the isocyanate derivative.

[0155] The amount of the portion derived from the hydrocarbon alcohol (α1) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, based on the portion derived from the active hydrogen compound.

[0156] The amount of the portion derived from the sugar alcohol / hydroxy acid modified product (α2) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, relative to the portion derived from the active hydrogen compound, and may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less.

[0157] The amount of the portion derived from the cationic active hydrogen compound (α3) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, based on the portion derived from the active hydrogen compound.

[0158] The amount of the portion derived from the other active hydrogen-containing compound (α4) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, based on the portion derived from the active hydrogen compound.

[0159] The amount of the portion derived from the raw isocyanate may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, based on the isocyanate derivative.

[0160] <Water repellent agent> The water repellent agent in the present disclosure is an agent that imparts water repellency to a substrate (e.g., a fiber substrate). The water repellent agent in the present disclosure can effectively impart water repellency and / or penetration resistance to the substrate, for example, can effectively impart both water repellency and penetration resistance.

[0161] The water repellent of the present disclosure includes the water repellent compound described above. One example of the water repellent is a water repellent containing a water repellent compound having a hydrocarbon group having 10 to 40 carbon atoms, wherein the water repellent compound includes an acrylic polymer and an isocyanate derivative, the isocyanate derivative has a water contact angle of 100° or more and includes a moiety derived from a cationic active hydrogen compound, and the weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20.

[0162] The water-repellent compound may be used as a water-repellent agent by itself, or may be used as a water-repellent agent in combination with other components as explained below.

[0163] The repellent agent of the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent agent of the present disclosure can impart water repellency to a substrate even without containing these fluorine compounds.

[0164] [Dispersant] The water repellent of the present disclosure may contain a dispersant.

[0165] The dispersant may be at least one selected from organic dispersants and inorganic dispersants. The dispersant may be non-anionic, and may be at least one selected from nonionic dispersants, cationic dispersants, amphoteric dispersants, and inorganic dispersants.

[0166] As the dispersant, an organic dispersant and an inorganic dispersant may be used individually, or a combination of an organic dispersant and an inorganic dispersant may be used.

[0167] An organic dispersant may be used as the dispersant. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant may refer to a surfactant.

[0168] The dispersant may be fluorine-free.

[0169] [Nonionic Dispersant] The dispersant may contain a nonionic dispersant, which may be a nonionic surfactant.

[0170] The nonionic dispersant may be a low molecular weight or a high molecular weight dispersant, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7500 or less, 5000 or less, 2500 or less, 750 or less, or 250 or less.

[0171] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0172] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0173] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to hexa-hydric (particularly di- to penta-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0174] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to hexa-hydric (particularly di- to penta-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0175] Examples of alkanolamides are those formed from fatty acids and alkanolamines. The alkanolamides may be monoalkanolamides or dialkanolamines. Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0176] The polyol may be a di- to penta-hydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (for example, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0177] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0178] The nonionic dispersant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0179] The nonionic dispersant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like. Among these, those in which the alkylene oxide adduct moiety and the polyalkylene glycol moiety have a structure of polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic dispersant does not have to contain an aromatic group.

[0180] The nonionic dispersant has the formula: 1 O-(CH ２ CH ２ O) p -(R 2 O) q -R 3 [In the formula, R 1is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms, 2 are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more.

[0181] R 1 R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. 1 Preferred specific examples of R include a lauryl group, a tridecyl group, and an oleyl group. 2 Examples of the nonionic dispersant are propylene and butylene. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, with the oxypropylene chain being preferred.

[0182] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C １２ -C １６ ) thiol, sorbitan mono fatty acid (C ７ -C １９ ) or alkyl (C １２ -C １８) condensation products with amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc.

[0183] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example 500 to 3,000. The nonionic dispersant may be a single type or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more.

[0184] [Cationic Dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a low molecular weight type (e.g., molecular weight of 2000 or less, particularly 10000 or less) or a high molecular weight type (e.g., molecular weight of 2000 or more). The cationic dispersant may be a compound having no amide group.

[0185] The cationic dispersant may be a low molecular weight or a high molecular weight dispersant, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may have a molecular weight of 100,000 or less, 10,000 or less, 7500 or less, 5000 or less, 2500 or less, 750 or less, or 250 or less.

[0186] The cationic dispersant may be an amine salt, a quaternary ammonium salt, or an oxyethylene adduct ammonium salt.Specific examples of the cationic dispersant include, but are not limited to, amine salt-type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline, and quaternary ammonium salt-type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride.

[0187] Preferred examples of cationic dispersants are: ２１ -N ＋ (-R ２２ ) (-R ２３ ) (-R ２４ ) X － [In the formula, R ２１ , R ２２ , R ２３ and R ２４ is a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group. ２１ , R ２２ , R ２３ and -R ２４ Specific examples of X are alkyl groups (e.g., methyl, butyl, stearyl, and palmityl). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). The cationic dispersant is particularly preferably a monoalkyltrimethylammonium salt (wherein the alkyl has 4 to 40 carbon atoms).

[0188] The cationic dispersant is preferably an ammonium salt. The cationic dispersant has the formula: １ ｐ -N ＋ R ２ ｑ X － [In the formula, R １ is C12 or more (e.g. C １２ ~C ５０ ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R ２is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH ３ , C ２ H ５ is particularly preferred), X is a halogen atom (for example), C １ ~C ４ where p is 1 or 2, q is 2 or 3, and p+q=4. １ may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0189] Specific examples of cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0190] [Anionic Dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0191] The anionic dispersant may be a low molecular weight or a high molecular weight dispersant, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may have a molecular weight of 100,000 or less, 10,000 or less, 7500 or less, 5000 or less, 2500 or less, 750 or less, or 250 or less.

[0192] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid type dispersants, phosphate mono- or diester type dispersants, and sulfosuccinate esters.

[0193] [Amphoteric Dispersant] The dispersant may contain an amphoteric dispersant, which may be an amphoteric surfactant.

[0194] The amphoteric dispersant may be a low molecular weight or a high molecular weight dispersant, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may have a molecular weight of 100,000 or less, 10,000 or less, 7500 or less, 5000 or less, 2500 or less, 750 or less, or 250 or less.

[0195] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0196] [Inorganic Dispersant] The dispersant may contain an inorganic dispersant.

[0197] The average primary particle size of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more, and may be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be hydrophilic particles.

[0198] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0199] [Reactive emulsifier] The dispersant may contain a reactive emulsifier. When the water-repellent compound is prepared (for example, an acrylic polymer is synthesized) in the presence of a reactive emulsifier, the water-repellent compound may be a polymer containing structural units derived from the reactive emulsifier.

[0200] If the water-repellent compound is a polymer containing structural units derived from a reactive emulsifier, the product stability of the aqueous dispersion (repellent composition) can be improved without reducing the water repellency.

[0201] The reactive emulsifier is an emulsifying dispersant having radical reactivity, that is, an emulsifier having one or more polymerizable unsaturated groups in the molecule, and is copolymerizable with the above-mentioned monomer component.

[0202] Examples of reactive emulsifiers include those described in JP 2017-25440 A. By using a reactive emulsifier, the product stability of the aqueous dispersion (water repellent) can be improved without reducing water repellency.

[0203] [Amount of Dispersant] The amount of dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the water-repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0204] [Liquid Medium] The water repellent agent in the present disclosure may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The water repellent agent may be a dispersion or a solution. The water repellent agent in the present disclosure may be a water-dispersed type and may contain at least water.

[0205] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., alcohol, polyols such as glycol-based solvents, ethers of polyols (e.g., monoethers), etc.). These may be used alone or in combination.

[0206] [Amount of Liquid Medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the water-repellent compound.

[0207] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the water-repellent compound.

[0208] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the water-repellent compound.

[0209] [Silicone] The water repellent agent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to achieve good water repellency as well as good texture and durability. The preparation of the water repellent compound (e.g., polymerization of monomers) may be carried out in the presence of silicone, or silicone may be added to the water repellent compound.

[0210] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.

[0211] The weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more, and may be 500,000 or less, 250,000 or less, 100,000 or less, or 50,000 or less.

[0212] [Amount of Silicone] The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the water-repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0213] [Wax] The water repellent agent according to the present disclosure may contain wax. By including wax, it is possible to impart good water repellency to the substrate.

[0214] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and vegetable wax, mineral wax, etc. Paraffin wax is preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane), and normal alkenes (e.g., 1-eicosane, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane). The number of carbon atoms in the compounds constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be from 200 to 2000, for example, from 250 to 1500, or from 300 to 1000. These may be used alone or in combination of two or more.

[0215] The melting point of the wax may be 40° C. or higher, 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher, preferably 55° C. or higher, more preferably 60° C. or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0216] [Amount of Wax] The amount of wax may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the water-repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0217] [Organic Acid] The water repellent of the present disclosure may contain an organic acid. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present disclosure, one organic acid may be used, or two or more organic acids may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0218] [Amount of Organic Acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the water-repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the water repellent agent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The water repellent agent may be acidic (pH 7 or less, for example, 6 or less).

[0219] [Curing Agent] The water repellent agent of the present disclosure may contain a curing agent (active hydrogen-reactive compound or active hydrogen-containing compound).

[0220] The curing agent (crosslinking agent) in the water repellent agent can effectively cure the water repellent compound. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive group of the water repellent compound. Examples of the active hydrogen-reactive compound include isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound include hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0221] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (e.g., a blocked polyisocyanate compound). A blocked isocyanate compound is a compound in which the isocyanate groups of an isocyanate compound are masked with a blocking agent to inhibit reaction.

[0222] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate, Aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0223] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0224] Examples of araliphatic polyisocyanates include araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0225] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0226] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretimines, isocyanurates, and iminooxadiazinediones. These may be used alone or in combination of two or more.

[0227] A blocked isocyanate compound is a compound in which the isocyanate group of an isocyanate compound is masked with a blocking agent to inhibit reaction. Examples of the isocyanate compound include the polyisocyanate compounds described above. Examples of the isocyanate compound include 4,4'-bisisocyanatophenylmethane, toluene diisocyanate, hexamethylene diisocyanate, diisocyanate trimers, and trimethylolpropane adducts. The blocking agent may be a known blocking agent, such as alcohols (e.g., secondary or tertiary alcohols), active methylene compounds, phenols, oximes, substituted pyrazoles, amine compounds, phenolic compounds, and lactams. The blocked isocyanate compound can be obtained by reacting an isocyanate compound with a blocking agent by a known method. After the reaction, the resulting mixture may be emulsified and dispersed using a surfactant by a known method. For example, after blocking 70 to 95% of all isocyanate groups of an isocyanate compound, the self-dispersibility of the blocked isocyanate compound may be improved by reacting an emulsifier (e.g., polyalkylene glycol, particularly polyethylene glycol) with the remaining isocyanate groups. Use of such a blocked isocyanate compound can impart effects such as improved washing durability to the water repellent agent and improved product stability.

[0228] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable in solution and can be used in the same solution as the water repellent.

[0229] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. The polyisocyanate compounds can be used alone or in combination of two or more.

[0230] An epoxy compound is a compound having an epoxy group. Examples of epoxy compounds include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. A chloromethyl group-containing compound is a compound having a chloromethyl group. An example of a chloromethyl group-containing compound is chloromethyl polystyrene. A carboxyl group-containing compound is a compound having a carboxyl group. Examples of a carboxyl group-containing compound are (poly)acrylic acid, (poly)methacrylic acid, etc.

[0231] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resins and methyl etherified melamine resins.

[0232] [Amount of Curing Agent] The amount of the curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the water-repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0233] [Other Components] The water repellent may contain other components in addition to the above components. Examples of other components include binder resins, anti-slip agents, sizing agents, paper strength agents, PVA, penetrating agents, organic acids, pigments, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, fragrances, polysaccharides, paper strength agents, flocculants, retention aids, coagulants, etc. These may be used alone or in combination of two or more. In addition to the above components, other components may include other water and / or oil repellents (for example, dendrimer-based water repellents (Ecoplus (manufactured by Rudolph))), dispersants, texture modifiers, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed regulators, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, anti-wrinkle agents when washed, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Chiba Specialty Chemicals), dye fixatives, 1,4-bis(3-aminopropanol), The following may be blended: anti-fading agents such as (propyl)piperazine; stain removers; fiber surface modifiers such as enzymes like cellulase, amylase, protease, lipase, and keratinase; foam inhibitors; silk protein powder, surface-modified products thereof, or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemicals), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)) that can impart silk texture and functionality such as moisture absorption and release; stain inhibitors (e.g., nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by GOO Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan, etc.). These may be used alone or in combination of two or more.

[0234] [Antistatic Agent] Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate ester salts, phosphonates, and phosphate ester salts; amphoteric antistatic agents such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, and nonionic antistatic agents such as aminoalcohols and its derivatives, glycerin and its derivatives, and polyethylene glycol and its derivatives. Ion-conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ionic conductive groups may also be used. These may be used alone or in combination of two or more.

[0235] [Preservatives] Preservatives can be used mainly to enhance antiseptic and bactericidal properties and maintain antiseptic properties during long-term storage. Examples of preservatives include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol.

[0236] [Ultraviolet Absorber] An ultraviolet absorber is a chemical agent that has the effect of protecting against ultraviolet rays, and is a component that absorbs ultraviolet rays and converts them into infrared rays, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0237] [Antibacterial Agent] An antibacterial agent is a component that has the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors resulting from microbial decomposition products. Examples of the antibacterial agent include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylenebiguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0238] [Deodorant] Examples of deodorants include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (e.g., zinc complex of trisodium methylglycine diacetate described in WO 2012 / 090580).

[0239] [Amount of Other Components] The amount of each of the other components or the total amount thereof may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the water-repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the water-repellent compound.

[0240] <Textile structure and manufacturing method thereof> The textile structure in the present disclosure refers to a treated textile product obtained by treating a textile substrate with a water repellent. The manufacturing method of the textile structure includes a treatment step of treating the substrate with the above-mentioned water repellent to adhere a water repellent compound, which is an active ingredient of the water repellent, to the textile substrate. "Treatment" means applying the water repellent to the substrate by immersion, spraying, coating, etc. The treatment causes the water repellent compound, which is an active ingredient of the water repellent, to adhere to the interior and / or surface of the substrate. Here, "adhesion" may be physical or chemical; for example, the water repellent compound may be physically or chemically modified (by reaction) with a hydroxy group of the substrate (e.g., fiber).

[0241] The water repellency of the fiber structure measured by the spray test method specified in JIS L1092:2009 may be grade 3 or higher, grade 4 or higher, or grade 5 or higher, preferably grade 4 or higher, and more preferably grade 5 or higher. The penetration rate of the fiber structure measured by the DIN 53924 test method may be 25 mm / 2 h or lower, 20 mm / 2 h or lower, 15 mm / 2 h or lower, 10 mm / 2 h or lower, or 5 mm / 2 h or lower, preferably 15 mm / 2 h or lower, and more preferably 10 mm / 2 h or lower.

[0242] [Substrate] The substrate to be treated with the water repellent agent of the present disclosure is not limited, but is preferably a textile product or a paper product, particularly a textile product.

[0243] Examples of substrates for textile products include natural fibers of animal or plant origin such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as cloth in the form of clothing (for example, water-repellent clothing such as raincoats) and carpets, but the treatment may also be applied to fibers, yarns, and intermediate textile products (for example, slivers or rovings) in a state prior to being made into cloth.

[0244] The air permeability of the fiber substrate is 20 cc / cm ２ / sec, 25cc / cm ２ / sec, 35cc / cm ２ / sec, 45cc / cm ２ / sec, 55cc / cm ２ / sec, 65cc / cm ２ / sec or more than 75cc / cm ２ The air permeability of the fiber substrate may be greater than 200 cc / cm ２ / sec or less, 180cc / cm ２ / sec or less, 160cc / cm ２ / sec or less, 140cc / cm ２ / sec or less, 120cc / cm ２ / sec or less, 100cc / cm ２ / sec or less, 80cc / cm ２ / sec or less, 60cc / cm ２ / sec or less than 40cc / cm ２ / sec or less. Even after the fiber substrate is treated with a water repellent (after the water-repellent compound is attached), there is usually no significant change in the air permeability, and the air permeability of the fiber substrate may be interpreted as the air permeability of the fiber structure. The fiber structure of the present disclosure can exhibit suitable water repellency and / or penetration resistance even when the fiber substrate has high air permeability.

[0245] The fabric density of the fiber base material is 100 g / m ２ Super, 125g / m ２ Super, 150g / m ２ Super, 175g / m ２ Super, 200g / m ２ Super, 225g / m ２ More than 250 g / m ２ The fabric density of the fibrous substrate may be greater than 500 g / m ２ Less than 450 g / m ２ Less than 400 g / m ２ Less than 350 g / m ２ Less than 300 g / m ２ Less than 250 g / m ２ Less than 200 g / m ２ Less than 150 g / m ２ Less than or equal to 125 g / m ２ The fabric density of the fiber substrate may be less than 1 / 2 mm. Even after the fiber substrate is treated with a water repellent (after the water repellent compound is attached), there is usually no significant change in the fabric density, and the fabric density of the fiber substrate may be interpreted as the fabric density of the fiber structure. The fiber structure of the present disclosure can exhibit suitable water repellency and / or penetration resistance even when the fabric density of the fiber substrate is high.

[0246] In particular, the fiber structure of the present disclosure is suitable for fabrics for applications requiring high breathability and high fabric density (for example, shoe fabrics).

[0247] Examples of substrates for paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine paper, recycled corrugated cardboard or deinked recycled paper, paper containers, paper molded articles, etc. Specific examples of paper products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating media, neutral white roll paper, neutral liner, rust-proof liner and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc., and suitable examples include food packaging materials and food containers.

[0248] Substrates that can be treated with the water repellent of the present disclosure are not limited to textiles or paper products, but also include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0249] When the substrate is glass, the produced glass product may be an optical component. A layer (or film), such as a hard coat layer or an anti-reflection layer, may be formed on the surface (outermost layer) of the glass substrate. The anti-reflection layer may be either a single-layer anti-reflection layer or a multi-layer anti-reflection layer. Examples of inorganic substances that can be used for the anti-reflection layer include SiO ２ , SiO, ZrO ２ , TiO ２ , TiO, Ti ２ O ３ , Ti ２ O ５ , Al ２ O ３ , Ta ２ O ５ , CeO ２ , MgO, Y ２ O ３ , SnO ２ , MgF ２ , W.O. ３ These inorganic substances may be used alone or in combination of two or more (for example, as a mixture). When a multi-layer antireflection layer is formed, the outermost layer may contain SiO ２ and / or SiO is preferably used. When the article to be manufactured is an optical glass component for a touch panel, a transparent electrode, for example, a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a portion of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomization film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, or the like, depending on its specific specifications.

[0250] [Treatment Method] The water repellent agent of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may involve dispersing and diluting the water repellent agent of the present disclosure in an organic solvent or water, as needed, and applying it to the interior and / or surface of the substrate by known methods such as dip coating, spray coating, foam coating, etc., followed by drying. After drying, a product is obtained in which the solid components of the water repellent agent are adhered. If necessary, the water repellent agent may be applied together with an appropriate crosslinking agent and cured. The water repellent agent of the present disclosure may also be used in combination with various additives, such as water and / or oil repellents, antislip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, and antifoaming agents. Examples of various additives may be the same as those described above under "Other Components." The concentration of the water repellent in the treatment agent to be brought into contact with the substrate may be varied as appropriate depending on the application, but may be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

[0251] The water repellent agent can be applied to the substrate by any of the known methods for treating a substrate with a liquid. The substrate may be immersed in a solution of the water repellent agent, or the solution may be applied or sprayed onto the substrate. The treated substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the substrate is paper, the water repellent agent may be coated on the paper, or the solution may be applied or sprayed onto the paper, or the water repellent agent may be mixed with a pulp slurry before papermaking. The treatment may be an external or internal addition treatment. Alternatively, the water repellent agent may be applied to textiles by a cleaning method, such as a laundry application or a dry cleaning method.

[0252] [Pretreatment of Textile Products] The textile product may be pretreated before being treated with the water repellent of the present disclosure. Pretreatment of the textile product can impart excellent fastness to the textile product after treatment with the water repellent.

[0253] Examples of pretreatments for textile products include cationization treatment by reaction with a reactive quaternary ammonium salt, anionization treatment such as sulfonation, carboxylation, and phosphate, acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment.

[0254] The method for pretreating a textile product is not limited, and the textile product can be pretreated by a conventionally known method. The pretreatment liquid may be dispersed and diluted in an organic solvent or water as necessary, and applied to the interior and / or surface of the textile product by a known method such as dip coating, spray coating, foam coating, etc., followed by drying. The pH and temperature of the pretreatment liquid may be adjusted depending on the desired degree of treatment. As an example of a method for pretreating a textile product, a method for pretreating a textile product with the above-mentioned treatment agent will be described in detail.

[0255] The pretreatment method for textile products is to add -SO ３ M １ (In the formula, M １ represents a monovalent cation), ２ (In the formula, M ２ represents a monovalent cation), and —O—P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) (hereinafter, also referred to as "specific functional groups").

[0256] M １ Examples of M include H, K, Na, and ammonium ions which may have a substituent. ２ Examples of X include H, K, Na, and ammonium ions which may have a substituent. １ or X２ When is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0257] Fibers containing the specific functional groups (hereinafter sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following methods: (i) A compound having the specific functional groups is attached to a fiber material. The attachment of the compound may be in a state where a portion of the compound is chemically bonded to a portion of the fiber, to the extent that a sufficient amount of the specific functional groups remains. (ii) Fibers are prepared in which the specific functional groups are directly introduced into the material that constitutes the fiber.

[0258] In the case of (i), for example, functional group-containing fibers can be obtained by a functional group introduction step in which a fiber material is treated with a pretreatment liquid containing one or more compounds having the above-mentioned specific functional groups.

[0259] The material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The form of the fiber material may be any form such as fiber (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, etc.

[0260] In this embodiment, from the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use a textile material containing polyamide and polyester as raw materials, and it is particularly preferable to use nylons such as nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate and polylactic acid, and mixed fibers containing these.

[0261] Above -SO ３ M １ A phenolic polymer can be used as the compound having the formula:

[0033] Such a phenolic polymer can be, for example, one containing at least one compound represented by the following general formula:

[0262] [In the formula, X２ Ha-SO ３ M ３ (In the formula, M ３ represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0263] [In the formula, M ４ represents a monovalent cation.

[0264] The above M ３ Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0265] The above M ４ Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0266] The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0267] Above - COOM ２ Examples of compounds having the formula include polycarboxylic acid polymers.

[0268] As the polycarboxylic acid polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer, or a commercially available product can be used.

[0269] Examples of methods for producing polycarboxylic acid polymers include adding a radical polymerization initiator to an aqueous solution of the above-mentioned monomer and / or its salt and heating the mixture at 30 to 150°C for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, or isopropyl alcohol, or an aqueous solvent such as acetone, may be added to the aqueous solution of the above-mentioned monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; redox-based polymerization initiators such as combinations of persulfates and sodium bisulfite; hydrogen peroxide; and water-soluble azo-based polymerization initiators. These radical polymerization initiators may be used alone or in combination. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.

[0270] In addition to the above-mentioned monomers, copolymerizable monomers can be used for radical polymerization. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. Preferred acrylates and methacrylates have a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used alone or in combination of two or more.

[0271] The carboxyl group in the polycarboxylic acid polymer may be free or may be neutralized with an alkali metal, an amine compound, etc. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0272] The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000, from the viewpoint of improving the water repellency of the resulting textile product.

[0273] As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (trade name, manufactured by Nicca Chemical Co., Ltd.) and "Ceropol PC-300" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0274] The above -O-P(O)(OX １ ) (OX ２ ) may be exemplified by phosphate ester compounds represented by the following general formula: [In the formula, X １ or X ２ is as defined above, and X ３ represents an alkyl group having 1 to 22 carbon atoms.

[0275] As the phosphate ester compound, phosphate monoesters, diesters and triesters, in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

[0276] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0277] As the phosphate ester compound, for example, commercially available products such as "Phosphanol ML-200" (trade name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0278] The pretreatment liquid containing one or more compounds having the specific functional group may be, for example, an aqueous solution of the compounds described above. The pretreatment liquid may also contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0279] Methods for treating textile materials with the pretreatment liquid include, for example, padding, immersion, spraying, and coating. Examples of padding include methods using padding devices described on pages 396-397 of "Textile Dyeing and Processing Dictionary" (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of "Color Dyeing Chemistry III" (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating include methods using coating machines described on pages 473-477 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of immersion include methods using batch dyeing machines described on pages 196-247 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). These machines include jet dyeing machines, air jet dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, and cheese dyeing machines. Examples of spray treatment include air spraying, in which the treatment liquid is atomized using compressed air, and methods using a hydraulic atomization air spray. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be adjusted appropriately, taking into account various conditions, such as the purpose and performance. Furthermore, when the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after application to remove the water. The drying method is not particularly limited, and may be either a dry heat method or a wet heat method. The drying temperature is also not particularly limited, and may be, for example, drying at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment at a temperature of 100 to 180°C for 10 seconds to 5 minutes may be performed after drying.

[0280] When the textile material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as the dyeing. However, when reduction soaping is carried out, there is a risk that the compound having the specific functional group (e.g., a phenolic polymer compound) adsorbed during the treatment may fall off, so it is preferable to carry out the treatment after reduction soaping after dyeing.

[0281] The treatment temperature in the immersion treatment can be 60 to 130° C. The treatment time can be 5 to 60 minutes.

[0282] In the functional group introduction step using a pretreatment liquid, the amount of the compound having the specific functional group attached is preferably 1.0 to 7.0 parts by weight per 100 parts by weight of the textile material. Within this range, durable water repellency and texture can both be achieved at high levels.

[0283] The pH of the pretreatment liquid may be adjusted to less than 7, for example, to a range of 3 to 5. The pH can be adjusted using a pH adjuster such as acetic acid or malic acid.

[0284] The pretreatment solution may contain a salt to effectively adsorb the compound having the specific functional group onto the fiber material through a salting-out effect. Examples of salts that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0285] In the functional group introduction step using a pretreatment liquid, it is preferable to remove the compound having the specific functional group that has been treated in excess. An example of a removal method is washing with water. By performing sufficient removal, it is possible to prevent the development of water repellency in the subsequent water-repellent treatment from being hindered, and in addition, the feel of the resulting textile product is improved. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fiber before contacting it with the above-mentioned treatment agent.

[0286] (ii) An example of a fiber in which the specific functional group is directly introduced into the material that constitutes the fiber is cationic dyeable polyester (CD-PET).

[0287] From the viewpoint of improving the water repellency of the resulting textile product, the functional group-containing fiber preferably has a surface zeta potential of −100 to −0.1 mV, more preferably −50 to −1 mV. The zeta potential of the fiber surface can be measured, for example, using a zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0288] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0289] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0290] <Production Examples 1 to 6: Synthesis of water-repellent compounds that are acrylic polymers> [Production Example 1] A 500 ml vessel was charged with 30 g of a water-soluble glycol solvent and 120 g of pure water as liquid media, 40 g of stearyl acrylate, 2 g of a sorbitan fatty acid ester as a surfactant, and 2 g of a cationic emulsifier and 6 g of polyoxyethylene alkyl ether as emulsifiers, and the mixture was heated to 80°C and stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes.

[0291] Next, this mixture was transferred to a 500 ml autoclave, and after purging with nitrogen, 0.2 g of lauryl mercaptan and 20 g of vinyl chloride were added as a chain transfer agent. Furthermore, 1 g of an azo group-containing water-soluble initiator was added as a polymerization initiator, and the mixture was heated to 60°C and reacted for 4 hours to obtain a polymer dispersion. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a solids concentration of 30%.

[0292] [Production Examples 2 to 4, 6] Aqueous dispersions were prepared in the same manner as in Production Example 1, except that the formulation was changed according to Table 1.

[0293] [Production Example 5] (Preparation of Silicone Polymer) A 200 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser was charged with 12 g of methyl hydrogen silicone oil (SiH:SiCH molar ratio measured by 1H NMR = 50:50) and 0.02 g of platinum catalyst. Next, 36 g of 1-hexacosene was charged into a dropping funnel, and while maintaining the temperature at 70°C, 1-hexacosene was added dropwise from the dropping funnel. After completion of the dropping, the mixture was further reacted at 70°C for 3 hours. The disappearance of the SiH peak was confirmed by infrared spectroscopy (IR), and 47 g of a solid silicone polymer was obtained.

[0294] Next, 28 g of silicone polymer, 5.6 g of water-soluble glycol solvent, 60 g of pure water, 1.7 g of sorbitan fatty acid ester, 0.7 g of polyoxyethylene alkyl ether, and 0.6 g of cationic emulsifier were charged into a 250 ml glass vessel, heated to 75° C., stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 10 minutes to obtain a silicone polymer dispersion. Then, pure water was added to prepare an aqueous silicone polymer dispersion with a solids concentration of 30 mass%.

[0295] (Preparation of acrylic polymer in the presence of silicone polymer) 25.5 g of water-soluble glycol solvent, 17 g of stearyl acrylate, 17 g of stearyl group-containing amide acrylate, 153 g of pure water, 1.7 g of sorbitan fatty acid ester, 1.7 g of cationic emulsifier, 5.1 g of polyoxyethylene alkyl ether, and 11 g of the silicone polymer synthesized above were placed in a 500 ml container and heated to 80 ° C., stirred at 2000 rpm with a homomixer for 1 minute, and then emulsified and dispersed with ultrasound for 15 minutes. The emulsified dispersion was transferred to a 500 ml autoclave, purged with nitrogen, and then charged with 0.17 g of lauryl mercaptan and 17 g of vinyl chloride. 0.85 g of azo group-containing water-soluble initiator was added, heated to 60 ° C., and reacted for 4 hours to obtain an aqueous dispersion of the polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a solids concentration of 30%.

[0296] The stearyl group-containing amide acrylate refers to stearic acid amide ethyl acrylate, and the polyoxyethylene alkylphenol refers to Ramtel PD-420 manufactured by Kao Corporation.

[0297] Production Examples 7 to 10: Production of Water-Repellent Compounds as Isocyanate Derivatives Production Example 7 Synthesis of Isocyanurate Derivative In a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, Inc., product name: Takenate 700), 0.25 parts by mass of 2,6-di(tert-butyl)-4-methylphenol (also known as dibutylhydroxytoluene, BHT, a hindered phenol-based antioxidant), and 0.25 parts by mass of tetraphenyl dipropylene glycol diphosphite (organic phosphite ester, cocatalyst) were mixed under a nitrogen atmosphere. 10.7 parts by mass of 1,3-butanediol was then added to the mixture, and nitrogen was introduced into the liquid phase for 1 hour. The mixture was then heated to 80°C and reacted for 3 hours, after which the temperature was lowered to 60°C. Subsequently, 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate was added as an isocyanuration catalyst, and the mixture was allowed to react for 1.5 hours. Subsequently, 0.04 parts by mass of o-toluenesulfonamide was added per 100 parts by mass of HDI. The reaction mixture was then passed through a thin-film distillation apparatus (temperature 150°C, vacuum degree 93.3 Pa) and distilled until the amount of residual HDI monomer was 0.5% or less, yielding an aliphatic polyisocyanate derivative (isocyanurate derivative of hexamethylene diisocyanate). The resulting isocyanurate derivative had an isocyanate group content of 20.9% and an average number of isocyanate functional groups of 3.0.

[0298] (Production of Hydrocarbon-Based Polyurethane) 100.20 g of the isocyanurate derivative obtained above, 67.60 g of Kalcol 8098 (stearyl alcohol, manufactured by Kao Corporation) as a long-chain active hydrogen compound, and 22.30 g of oleic alcohol were mixed in a reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, and the mixture was reacted in a nitrogen atmosphere at 110°C for 4 hours until the isocyanate group concentration reached 3.67%. The reaction solution was then cooled to 80°C, and 9.90 g of N-methyldiethanolamine as a cationic active hydrogen compound was added, followed by a reaction at 80°C for 1 hour. Next, 50.00 g of methyl ethyl ketone was added as a solvent, and the mixture was reacted at 80°C until disappearance of the isocyanate groups was confirmed by infrared absorption spectroscopy. Next, 57.69 g of methyl ethyl ketone was added to the reaction solution, the temperature was raised to 80°C, and the reaction solution was mixed until completely dissolved, after which it was cooled to 75°C. Thereafter, 18.96 g of acetic acid was added as an acid compound to neutralize the mixture. Next, while maintaining the reaction solution at 75°C, 800.0 g of ion-exchanged water heated to 70°C was gradually added to emulsify (internal emulsification). The mixture was then evaporated in an evaporator at a water bath temperature of 60°C under reduced pressure until the solids concentration reached 20 wt% or more. The solids concentration excluding the acid compound (acetic acid) was then adjusted with ion-exchanged water to 20 wt%, thereby obtaining an aqueous dispersion containing polyurethane.

[0299] [Production Example 8] 116 g of sorbitan tristearate and 150 g of 4-methyl-2-pentanone (MIBK) were charged into a 500 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser. Next, to remove excess water vapor from this mixture, the mixture was stirred while maintaining the temperature of the mixture at 70°C, refluxed for 1 hour, and then allowed to cool to 50°C. Then, while maintaining stirring, 30 g of Desmodur N-100 (a biuret derivative of hexamethylene diisocyanate, Covestro) was added dropwise to the mixture using a dropping funnel. After completion of the dropwise addition, one drop of dibutyltin dilaurate was added as a catalyst, and the mixture was allowed to react at 80°C for 1 hour. Next, 25 g of sorbitan monostearate was added, and the mixture was allowed to react for an additional 4 hours at 80°C. The reaction mixture was then cooled to 60°C, and the recovered mixture was slowly mixed with water at 60°C containing an arbitrary amount of cationic emulsifier and polyoxyethylene alkyl ether. The mixture was stirred at 6000 rpm for 1 minute using a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. The solvent (MIBK) was then removed under reduced pressure, and pure water was added to adjust the concentration, yielding an aqueous dispersion containing polyurethane with a solids concentration of 20%.

[0300] [Production Example 9] 150 g of methyl ethyl ketone (MEK) and 51 g of stearyl alcohol were charged into a 500 mL four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser. Next, in order to remove excess water vapor from this mixture, the mixture was stirred while maintaining the temperature of the mixture at 70 ° C., refluxed for 1 hour, and then allowed to cool to 50 ° C. Then, 30 g of Desmodur N3200A (a biuret derivative of hexamethylene diisocyanate, manufactured by Covestro) was added to the mixture, and the mixture was further reacted at 80 ° C. for 4 hours. Next, after cooling to 60 ° C., the reaction solution was recovered, and the reaction solution was slowly mixed with water at 60 ° C. containing an arbitrary amount of polyoxyethylene alkyl ether. This mixture was stirred at 6000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. Next, the solvent (MEK) was removed under reduced pressure, and then pure water was added to adjust the concentration, to obtain an aqueous dispersion containing polyurethane with a solids concentration of 20%.

[0301] [Production Example 10] A 1000 mL flask was charged with 190.6 g of trimethylolpropane, 808.2 g of stearic acid, and 1.2 g of p-toluenesulfonic acid, and a dehydration reaction was carried out for 3 hours at 140 to 210°C under a nitrogen stream to obtain a product. The acid value and hydroxyl value of the obtained product were measured, and the acid value was 1.8 mgKOH / g and the hydroxyl value was 89 mgKOH / g. In a separate container, 715.5 g of the above product, 180.2 g of hexamethylene diisocyanate, and 1.3 g of a bismuth catalyst (Neostan U-600, manufactured by Nitto Kasei Co., Ltd.) were placed, and the reaction was carried out at 80°C for 5 hours. The reaction was carried out until the NCO% reached 5.0. After the reaction, the temperature was lowered to 40°C, and then 103.0 g of 3,5-dimethylpyrazole was added and the reaction was carried out at 40°C for 1 hour to obtain an isocyanate derivative. In the isocyanate derivative, two hydroxy groups in trimethylolpropane form ester groups with stearic acid, and one hydroxy group forms a urethane bond with hexamethylene diisocyanate, one end of which is protected with 3,5-dimethylpyrazole.

[0302] In a 500 mL stainless steel container, 40 g of the isocyanate derivative obtained above, 50 g of methyl ethyl ketone, 10 g of polyglycerol fatty acid ester, and 5 g of a cationic emulsifier were placed and dissolved by heating to 50° C. Next, 295 g of hot water at 80° C. was added, and the mixture was emulsified for 20 minutes using an ultrasonic emulsifier while maintaining the temperature at 80° C. After cooling, a 10% dispersion of the isocyanate derivative was obtained.

[0303] Examples and Comparative Examples The dispersions obtained in the above production examples were diluted with tap water to the compositions shown in Table 2, to prepare 1000 g of test liquids with a solid content concentration of 1.0 mass %.

[0304] Next, a test cloth shown in Table 2 was immersed in this test solution, passed through a mangle, and then passed through a pin tenter at 160°C for 1 minute, whereupon it was dried and cured. Thereafter, the following water repellency test and penetration resistance test were carried out.

[0305] The dendrimer-based water repellent used was Ecoplus (manufactured by Rudolph Co., Ltd.) The curing agent used was a 40% by mass aqueous dispersion of a dimethylpyrazole block copolymer of HDI (hexamethylene diisocyanate) trimer.

[0306] The test procedure was as follows: The results are shown in Table 2.

[0307] [Water repellency test] Evaluation was performed and graded using the spray test method specified in JIS L1092:2009 (AATCC-22) "Test method for waterproofness of textile products." Water repellency: Condition 5: No adhesion or wetness on the surface 4: Slight adhesion or wetness on the surface 3: Partial wetness on the surface 2: Wetness on the surface 1: Wetness on the entire surface 0: Complete wetness on both the front and back surfaces

[0308] [Penetration Resistance Test] The penetration resistance test was evaluated according to the method specified in DIN 53924. Specifically, the test was performed as follows. A fiber structure cut to a size of 3 cm wide and 8 cm long was prepared, and a water level line was marked 1 cm from the bottom. Next, the fiber structure was hung, and the bottom was immersed in water up to the water level line and left to stand for 2 hours. After 2 hours, the length (mm) of the part wetted by capillary action (length from the water level line) was measured.

[0309] [Water Contact Angle Test] The water contact angle of the water-repellent compound was determined by spin-coating a chloroform solution of the water-repellent compound having a solids concentration of 1.0% on a silicon wafer substrate, dropping 2 μL of water onto the coating film, and measuring the contact angle 1 second after the drop had landed.

[0310] [Air permeability test] Measurement was carried out according to JIS L1096:2010 8.26.1 Method A "Fragile method".

[0311] [Measurement of Fabric Density] Ten pieces of fabric were cut into 10 cm x 10 cm pieces, and the weights were measured to determine the average weight. From the average weights, the fabric density (g / m) was calculated. ２ was calculated. [Table 1]

[0312] [Table 2]

[0313] In polyester 1, the breathability is 80 cc / cm ２ / sec to 88cc / cm after repellent treatment ２ / sec, and the fabric density is 230 g / m ２ After repellent treatment: 232 g / m ２ In nylon 1, the air permeability increased to 70 cc / cm ２ / sec to 77cc / cm after repellent treatment ２ / sec, and the fabric density is 200 g / m ２ After repellent treatment, 201 g / m ２ In polyester 2, the air permeability increased to 80 cc / cm ２ / sec to 86cc / cm after repellent treatment ２ / sec, and the fabric density is 40 g / m ２ There was no significant difference between the Examples and Comparative Examples.

Claims

1. A fiber structure in which a water-repellent compound having a hydrocarbon group having 6 to 40 carbon atoms is attached to a fiber base material, and the air permeability is 20 cc / cm ２ / sec or more, and the fabric density is 100 g / m ２ A super fiber structure.

2. The fiber structure according to claim 1, wherein the water-repellent compound is at least one selected from the group consisting of acrylic polymers and isocyanate derivatives.

3. The fiber structure according to claim 2, wherein the water-repellent compound comprises the acrylic polymer, and the acrylic polymer has a repeating unit derived from a multicarbonyl monomer having one ethylenically unsaturated double bond and two or more carbonyl groups.

4. The fiber structure according to claim 2 or 3, wherein the water-repellent compound contains the isocyanate derivative, and the isocyanate derivative has a portion derived from a cationic active hydrogen compound.

5. The fiber structure according to any one of claims 2 to 4, wherein the water-repellent compound comprises the acrylic polymer and the isocyanate derivative.

6. The fiber structure according to any one of claims 2 to 5, wherein the water-repellent compound comprises the acrylic polymer and the isocyanate derivative having a water contact angle of 100° or more and having a portion derived from a cationic active hydrogen compound.

7. The fiber structure according to any one of claims 2 to 6, wherein the weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20.

8. The fiber structure according to any one of claims 1 to 7, having a water repellency of grade 4 or higher according to a spray test method specified in JIS L1092:2009, and a penetration rate of less than 10 mm / 2 h according to a DIN 53924 test method.

9. The water-repellent compound includes an acrylic polymer and an isocyanate derivative, the acrylic polymer includes a monomer (a) having a hydrocarbon group having 6 to 40 carbon atoms, and the monomer (a) is represented by the formula: CH2=C(-X ａ )-C(=O)-Y ａ (R ａ ) ｋ [In the formula, R ａ are each independently a hydrocarbon group having 6 to 40 carbon atoms; ａ is a hydrogen atom, a monovalent organic group or a halogen atom; Y ａ is a divalent to tetravalent group, and k is 1 to 3.], the amount of repeating units derived from the monomer (a) is 50% by weight or more relative to the acrylic polymer, the isocyanate derivative has a water contact angle of 100° or more and has a portion derived from a cationic active hydrogen compound, and the weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20.

10. A water repellent comprising a water repellent compound having a hydrocarbon group having 6 to 40 carbon atoms, the water repellent compound comprising an acrylic polymer and an isocyanate derivative, the isocyanate derivative having a water contact angle of 100° or more and comprising a portion derived from a cationic active hydrogen compound, and the weight ratio of the acrylic polymer to the isocyanate derivative being 50 / 50 to 80 / 20.

11. The water repellent according to claim 10, wherein the acrylic polymer has a repeating unit derived from a multicarbonyl monomer having one ethylenically unsaturated double bond and two or more carbonyl groups.

12. Air permeability: 20cc / cm ２ / sec and fabric density 100g / m ２ A method for producing a fiber structure, comprising a step of treating a fiber substrate with a water repellent agent containing a water repellent compound having a hydrocarbon group having 6 to 40 carbon atoms.

13. Air permeability: 20cc / cm ２ 1. A method for producing a fiber structure, comprising the step of treating a fiber substrate having a water repellent of more than 100° / sec with a water repellent, wherein the water repellent contains a water repellent compound having a hydrocarbon group having 6 to 40 carbon atoms, the water repellent compound contains an acrylic polymer and an isocyanate derivative, and the isocyanate derivative has a water contact angle of 100° or more and contains a portion derived from a cationic active hydrogen compound.

14. The method for producing a fiber structure according to claim 13, wherein the weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20.

15. A method for producing a fiber structure according to claim 13 or 14, wherein the water-repellent compound comprises the acrylic polymer, and the acrylic polymer has a repeating unit derived from a multicarbonyl monomer having one ethylenically unsaturated double bond and two or more carbonyl groups.

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