Water-repellent agent composition

Abstract

The present invention provides a water-repellent agent composition which contains a polymer (A) having a repeating unit that is derived from a silicon-containing monomer represented by formula CH2=C(-Ra)-X-SiZ3 (in the formula, Ra represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, X represents a divalent group that is composed of one or more selected from the group consisting of X1 and X2, X1 represents a group that is composed of one or more selected from the group consisting of -O-, -C(=O)-, and -NR'- (wherein each R' independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), X2 represents a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, each Z independently represents a hydrocarbon group having 1 to 10 carbon atoms or –(O-SiZ1 2)n-O-SiZ2 3, each Z1 independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ11 3, each Z11 independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ111 3, each Z111 independently represents a hydrocarbon group having 1 to 10 carbon atoms, each Z2 independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ21 3, each Z21 independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ211 3, each Z211 independently represents a hydrocarbon group having 1 to 10 carbon atoms, and each n independently represents an integer of 0 to 196) and a dispersant (B), wherein: the polymer (A) contains the repeating unit that is derived from the silicon-containing monomer in an amount of 90% by weight or more based on the weight of the polymer (A); and polymer (A) has a number average molecular weight of 60,000 to 4,000,000 inclusive. The water-repellent agent composition is capable of imparting both good water repellency and good slip resistance to a base material (particularly, a fiber product).

Description

Water repellent composition

[0001] The present disclosure relates to a water repellent composition.

[0002] BACKGROUND ART Non-fluorine-based water repellents have been developed as water repellents for imparting water repellency to substrates (particularly textile products).

[0003] Chinese Patent No. 116289217

[0004] When conventional water repellents are used in textile products, there is a risk that the stitching may slip, reducing the reliability of the textile product.

[0005] An object of the present disclosure is to provide a water repellent composition that can impart both good water repellency and good slip resistance to textile products.

[0006] The present disclosure includes the following aspects: [Item 1] A compound represented by the following formula: CH ２ = C (-R ａ )-X-SiZ ３ [In the formula: R ａ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and X is X １ and X ２ is a divalent group consisting of one or more members selected from the group consisting of １ is a group consisting of one or more selected from the group consisting of —O—, —C(═O)—, and —NR′— (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), and X ２ is a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, and each Z is independently a hydrocarbon group having 1 to 10 carbon atoms or -(O-SiZ １ ２ ) ｎ -O-SiZ ２ ３ and Z １ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ １１ ３ and Z １１ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ １１１ ３ and Z １１１are each independently a hydrocarbon group having 1 to 10 carbon atoms; Z ２ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ ２１ ３ and Z ２１ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ ２１１ ３ and Z ２１１ and n is each independently an integer of 0 to 196. A water repellent composition comprising: a polymer (A) containing repeating units derived from a silicon-containing monomer represented by the formula: and a dispersant (B), wherein the amount of repeating units derived from the silicon-containing monomer in the polymer (A) is 90 wt % or more of the weight of the polymer (A), and the number average molecular weight of the polymer (A) is 60,000 or more and 4,000,000 or less. [Item 2] X is -X １ -X ２ - [wherein, X １ is —C(═O)—O—, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′—C(═O)—O—, —NR′—C(═O)—NR′—, —C(═O)—, or —C(═O)—NR′— (wherein R′ in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), X ２ [Item 3] The water repellent composition according to Item 1, wherein Z is a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms. １ are each independently -OSiZ １１ ３ and Z １１ are each independently an alkyl group having 1 to 3 carbon atoms; Z ２ are each independently -OSiZ ２１ ３ and Z ２１ [Item 4] The water repellent composition according to Item 1 or 2, wherein X are each independently an alkyl group having 1 to 3 carbon atoms. ２[Item 5] The water repellent composition according to any one of Items 1 to 3, wherein n is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms. [Item 6] The water repellent composition according to any one of Items 1 to 4, wherein n is 0. [Item 6] The water repellent composition according to any one of Items 1 to 5, wherein the polymer (A) contains repeating units derived from the silicon-containing monomer in an amount of 96 wt% or more of the weight of the polymer (A). [Item 7] The water repellent composition according to any one of Items 1 to 6, wherein the number average molecular weight of the polymer (A) is 2,000,000 or less. [Item 8] The water repellent composition according to any one of Items 1 to 7, wherein the dispersant (B) comprises a cationic dispersant. [Item 9] The water repellent composition according to any one of Items 1 to 8, wherein the dispersant (C) comprises at least one compound selected from the group consisting of vinyl polymers, isocyanate derivatives, waxes, and silicones. [Item 10] The water repellent composition according to Item 9, wherein the amount of the polymer (A) in the water repellent composition is 5% by weight to 95% by weight based on the total amount of the polymer (A) and the amount of the compound (C). [Item 11] The water repellent composition according to Item 9 or 10, wherein the compound (C) is a polymer containing a repeating unit derived from a hydrocarbon group-containing monomer having a hydrocarbon group having 2 to 40 carbon atoms. [Item 12] The hydrocarbon group-containing monomer is a compound represented by the following formula: CH ２ = C (-R ｂ )-C(=O)-R ｃ - (R ｄ ) ｋ [In the formula, R ｂ is a hydrogen atom, a monovalent organic group or a halogen atom, R ｃ represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -S-, -C(=O)-, -S(=O) ２ - and -NR Ｃ１ - (R Ｃ１ is a divalent to tetravalent group consisting of at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms; k is an integer of 1 to 3; R ｄ and each independently represents a hydrocarbon group having 2 to 40 carbon atoms. １ -X ２- [wherein, X １ is —C(═O)—O—, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′—C(═O)—O—, —NR′—C(═O)—NR′—, —C(═O)—, or —C(═O)—NR′— (wherein R′ in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), X ２ is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms; n is 0; Z ２ are each independently an alkyl group having 1 to 3 carbon atoms, and are represented by the following formula: CH ２ = C (-R ｂ )-C(=O)-R ｃ - (R ｄ ) ｋ [In the formula, R ｂ is a hydrogen atom, a monovalent organic group or a halogen atom, R ｃ represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -S-, -C(=O)-, -S(=O) ２ - and -NR Ｃ１ - (R Ｃ１ is a divalent to tetravalent group consisting of at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms; k is an integer of 1 to 3; R ｄ is a hydrocarbon group having 2 to 40 carbon atoms.], and the amount of the polymer (A) in the water repellent composition is 5% by weight to 95% by weight based on the total amount of the polymer (A) and the amount of the compound (C). [Item 14] The water repellent composition according to Item 1, further comprising a compound (C) which is a polymer containing a repeating unit derived from a hydrocarbon group-containing monomer represented by the formula: ａ is a hydrogen atom or a methyl group, and X is -X １ -X ２ - [wherein, X １ is —C(═O)—O—, —O—C(═O)—, and X ２ is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms; n is 0; Z ２are each independently an alkyl group having 1 to 3 carbon atoms, the polymer (A) contains repeating units derived from the silicon-containing monomer in an amount of 97 wt % or more of the weight of the polymer (A), and the number average molecular weight of the polymer (A) is 100,000 or more and 2,000,000 or less, and the dispersant (B) is a cationic dispersant. [Item 15] A method for producing a textile product, comprising applying the water repellent composition according to any one of Items 1 to 14 to a textile substrate. [Item 16] A method for producing a textile product, comprising applying a water repellent composition according to any one of Items 1 to 14 to a textile substrate. [Item 16] A method for producing a textile product, comprising applying a water repellent composition according to any one of Items 1 to 14 to a textile substrate before applying the water repellent composition to the textile substrate. ３ M １ (In the formula, M １ represents a monovalent cation), ２ (In the formula, M ２ represents a monovalent cation), and １ ) (OX ２ ) (wherein, X １ and X ２ [Item 17] A method for producing a textile product according to Item 15, comprising a step of providing one or more functional groups selected from the group consisting of monovalent groups represented by the formula: [wherein each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms]. [Item 18] A textile product comprising a textile substrate to which the water repellent composition according to any one of Items 1 to 13 has adhered. [Item 19] A textile product comprising a water repellent composition according to any one of Items 1 to 17, wherein the water repellent composition is a fibrous substrate. ３ M １ (In the formula, M １ represents a monovalent cation), ２ (In the formula, M ２ represents a monovalent cation), and 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.

[0007] The water repellent composition of the present disclosure can impart both good water repellency and good slip resistance to a substrate (particularly a textile product).

[0008] <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, and an "organic group" refers to a group containing carbon. Such organic groups are not particularly limited, but may be hydrocarbon groups or derivatives thereof. A hydrocarbon group derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the end or molecular chain of the hydrocarbon group.

[0009] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C １－２０ The hydrocarbon group may be, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or the like. 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.

[0010] In this specification, when a term (symbol) that may appear multiple times in a chemical structure is defined, that definition applies independently to each occurrence, unless otherwise stated, regardless of whether "independently in each occurrence," "independently each occurrence," or similar expressions are explicitly stated.

[0011] 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.

[0012] <Water repellent composition> The water repellent composition according to the present disclosure is a water repellent composition represented by the following formula: CH ２ = C (-R ａ )-X-SiZ ３ [In the formula: R ａ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and X is X １ and X２ is a divalent group consisting of one or more members selected from the group consisting of １ is a group consisting of one or more selected from the group consisting of —O—, —C(═O)—, and —NR′— (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), and X ２ is a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, and each Z is independently a hydrocarbon group having 1 to 10 carbon atoms or -(O-SiZ １ ２ ) ｎ -O-SiZ ２ ３ and Z １ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ １１ ３ and Z １１ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ １１１ ３ and Z １１１ are each independently a hydrocarbon group having 1 to 10 carbon atoms; Z ２ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ ２１ ３ and Z ２１ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ ２１１ ３ and Z ２１１ are each independently a hydrocarbon group having 1 to 10 carbon atoms, and each n is independently an integer of 0 to 196.] The polymer (A) contains 90 wt % or more of the silicon-containing monomer based on the weight of the polymer (A), and the number average molecular weight of the polymer (A) is 60,000 or more and 4,000,000 or less.

[0013] The water repellent composition according to the present disclosure has the above-described characteristics and can impart liquid repellency (water repellency, oil repellency, oil resistance, and / or water resistance) to a substrate (e.g., a fiber substrate, a paper substrate). The polymer (A) according to the present disclosure can function as at least one selected from the group consisting of a water repellent, an oil repellent, an oil-resistant agent, and a water-resistant agent. The water repellent composition according to the present disclosure can effectively impart oil resistance (oil repellency) and / or water resistance (water repellency) to a substrate, and can, for example, effectively impart both oil resistance and water resistance.

[0014] By virtue of having the above-described characteristics, the water repellent composition of the present disclosure can be adhered to a substrate (e.g., a fiber substrate, a paper substrate) and can impart both good liquid repellency (water repellency, oil repellency, oil resistance, and / or water resistance) and good slip resistance to the substrate.

[0015] [(A) Polymer] The polymer (A) of the present disclosure will be described. The polymer (A) contains a repeating unit derived from a silicon-containing monomer. The polymer (A) is a polymer obtained by polymerizing a monomer. Here, the monomer may be a compound having a polymerizable carbon-carbon double bond (ethylenically unsaturated double bond) (>C=C<), and may be a monomer containing a vinyl group, a vinylene group, a vinylidene group, an acryloyl group, a methacryloyl group, or a derivative group thereof.

[0016] The polymer (A) of the present disclosure has the above characteristics and can impart not only liquid repellency (water repellency, oil repellency, oil resistance, and / or water resistance) but also slip resistance to a substrate (e.g., a fiber substrate, a paper substrate).

[0017] The polymer (A) of the present disclosure may be non-fluorinated. Specifically, the polymer (A) of the present disclosure may not have a perfluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 6 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, or a fluorine atom.

[0018] [Silicon-containing monomer] The polymer (A) of the present disclosure contains a repeating unit derived from a silicon-containing monomer. The silicon-containing monomer is represented by the following formula: CH ２ = C (-R ａ )-X-SiZ ３

[0019] [R ａ ] R ａ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. The hydrocarbon group having 1 to 5 carbon atoms may be a hydrocarbon group having 1 to 3 carbon atoms or may be a methyl group. ａ is preferably a hydrogen atom or a methyl group.

[0020] [X] X is X １ and X ２ is a divalent group consisting of one or more members selected from the group consisting of １ is a group consisting of one or more selected from the group consisting of -O-, -C(=O)-, and -NR'- (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, 1 to 5, or 1 carbon atom)), and X ２ is a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms.

[0021] The molecular weight of X may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more. The molecular weight of X may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0022] (X １ ) X １ is a non-hydrocarbon linker.

[0023] X １ The molecular weight of X may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less. １ may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.

[0024] X １ is a group consisting of one or more selected from the group consisting of —O—, —C(═O)—, and —NR′— (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, 1 to 5, or 1 carbon atom)).

[0025] X１ Examples of include —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—, —C(═O)—O—, —C(═O)—NR′—, and the like, wherein R′ in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, 1 to 5, or 1 carbon atom).

[0026] In one aspect, X １ may be —C(═O)—O— or —C(═O)—NR′—, where R′ may be independently in each occurrence a hydrogen atom or a hydrocarbon group of 1 to 3 carbon atoms.

[0027] (X ２ ) X ２ is a direct bond or a hydrocarbon group which may have a substituent. Such a hydrocarbon group is a divalent hydrocarbon group.

[0028] X ２ The number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, 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, and may be 40 or less, 38 or less, 35 or less, 32 or less, 30 or less, 28 or less, or 25 or less.

[0029] X ２ The hydrocarbon group of X may be branched or linear. ２ The hydrocarbon group may be an aliphatic hydrocarbon group, in particular a saturated aliphatic hydrocarbon group.

[0030] In one aspect, X ２ The hydrocarbon group may have 1 or more, 2 or more, or 3 or more carbon atoms, and may have 6 or less, 5 or less, or 4 or less carbon atoms.

[0031] In one aspect, X ２ is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, preferably a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms.

[0032] X ２The hydrocarbon group in may have a substituent. Examples of the substituent include -OR', -N(R') ２ , -COOR', and halogen atoms (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0.

[0033] X ２ Specific examples of -(CH ２ ) ｑ -. q is an integer from 1 to 22. q may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more. q may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0034] (Examples of X) Examples of X include -X １ -, -X １ -X ２ -, -X １ -X ２ -X １ -, -X １ -X ２ -X １ -X ２ -, -X ２ -, -X ２ -X １ -, -X ２ -X １ -X ２ -, -X ２ -X １ -X ２ -X １ -, etc. Preferred examples of X include -X １ -X ２ -, -X ２ - are listed.

[0035] In one aspect, X is -X １ -X ２ - [wherein, X １is —C(═O)—O—, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′—C(═O)—O—, —NR′—C(═O)—NR′—, —C(═O)—, or —C(═O)—NR′— (wherein R′ in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), X ２ is a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, preferably a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, and more preferably a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms.

[0036] In one aspect, X is —C(═O)—O—(CH ２ ) ｑ - or -C(=O)-NR'-(CH ２ ) ｑ -, R' may be, independently in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and q may be 1 or more, 2 or more, or 3 or more, and may be 6 or less, 5 or less, 4 or less, or 3 or less.

[0037] [Z] Z is a group that bonds to Si of the silicon-containing monomer.

[0038] Each Z is independently a hydrocarbon group having 1 to 10 carbon atoms or -(O-SiZ １ ２ ) ｎ -O-SiZ ２ ３ is.

[0039] The hydrocarbon group having 1 to 10 carbon atoms may be a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0040] In one embodiment, each Z is independently —(O—SiZ １ ２ ) ｎ -O-SiZ ２ ３ It may be.

[0041] (Z １ ) Z １are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ １１ ３ is.

[0042] Z １ is a hydrocarbon group having 1 to 10 carbon atoms, the number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more, and may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0043] In one aspect, Z １ may be a methyl group or an ethyl group, preferably a methyl group.

[0044] The above OSiZ １ ２ Two Zs in １ may all be hydrocarbon groups having 1 to 10 carbon atoms, or may all be —OSiZ １１ ３ or a hydrocarbon group having 1 to 10 carbon atoms and —OSiZ １１ ３ It may be.

[0045] (Z １１ ) Z １１ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ １１１ ３ is.

[0046] Z １１ is a hydrocarbon group having 1 to 10 carbon atoms, the number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more, and may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0047] In one aspect, Z １１ may be a methyl group or an ethyl group, preferably a methyl group.

[0048] Above -OSiZ １１ ３ The three Zs in １１ may all be hydrocarbon groups having 1 to 10 carbon atoms, or may all be —OSiZ １１１ ３ or may be two hydrocarbon groups having 1 to 10 carbon atoms and —OSiZ１１１ ３ or one hydrocarbon group having 1 to 10 carbon atoms and —OSiZ １１１ ３ There may be two.

[0049] (Z １１１ ) Z １１１ are each independently a hydrocarbon group having 1 to 10 carbon atoms.

[0050] Z １１１ is a hydrocarbon group having 1 to 10 carbon atoms, the number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more, and may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0051] In one aspect, Z １１１ may be a methyl group or an ethyl group, preferably a methyl group.

[0052] (Z ２ ) Z ２ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ ２１ ３ is.

[0053] Z ２ is a hydrocarbon group having 1 to 10 carbon atoms, the number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more, and may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0054] In one aspect, Z ２ may be a methyl group or an ethyl group, preferably a methyl group.

[0055] The above OSiZ ２ ３ The three Zs in ２ may all be hydrocarbon groups having 1 to 10 carbon atoms, or may all be —OSiZ ２１ ３ or may be two hydrocarbon groups having 1 to 10 carbon atoms and —OSiZ ２１ ３ or one hydrocarbon group having 1 to 10 carbon atoms and —OSiZ ２１ ３There may be two.

[0056] (Z ２１ ) Z ２１ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ ２１１ ３ is.

[0057] Z ２１ is a hydrocarbon group having 1 to 10 carbon atoms, the number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more, and may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0058] In one aspect, Z ２１ may be a methyl group or an ethyl group, preferably a methyl group.

[0059] Above -OSiZ ２１ ３ The three Zs in ２１ may all be hydrocarbon groups having 1 to 10 carbon atoms, or may all be —OSiZ ２１１ ３ or may be two hydrocarbon groups having 1 to 10 carbon atoms and —OSiZ ２１１ ３ or one hydrocarbon group having 1 to 10 carbon atoms and —OSiZ ２１１ ３ There may be two.

[0060] (Z ２１１ ) Z ２１１ are each independently a hydrocarbon group having 1 to 10 carbon atoms.

[0061] Z ２１１ is a hydrocarbon group having 1 to 10 carbon atoms, the number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more, and may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0062] In one aspect, Z ２１１ may be a methyl group or an ethyl group, preferably a methyl group.

[0063] (Examples of Z) Z in one embodiment １ and Z ２About Z １ are each independently -OSiZ １１ ３ and Z １１ are each independently an alkyl group having 1 to 3 carbon atoms; Z ２ are each independently -OSiZ ２１ ３ and Z ２１ are each independently an alkyl group having 1 to 3 carbon atoms.

[0064] (n) Each n is independently an integer of 0 to 196. n may be 0 or more, 5 or more, 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, or 100 or more, or may be 196 or less, 190 or less, 180 or less, 170 or less, 160 or less, 150 or less, 140 or less, 130 or less, 120 or less, 110 or less, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, 20 or less, 10 or less, 5 or less, 3 or less, 2 or less, or 1 or less.

[0065] In one embodiment, -SiZ ３ In the formula (I), n of at least one Z may be 0, n of at least two Z may be 0, or n of all Z may be 0.

[0066] [Examples of silicon-containing monomers] Examples of silicon-containing monomers include those represented by the following formula: ２ = C (-R ａ )-X １ -(CH ２ ) ｑ -Si(-O-SiZ ２ ３ ) ３ [In the formula: R ａ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and X １ is a group consisting of one or more selected from the group consisting of —O—, —C(═O)—, and —NR′— (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), q is an integer of 1 to 22, and Z ２ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ２１ ３ and Z ２１ are each independently a hydrocarbon group having 1 to 10 carbon atoms.]

[0067] In the above example, R ａ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. The hydrocarbon group having 1 to 5 carbon atoms may be a hydrocarbon group having 1 to 3 carbon atoms or may be a methyl group.

[0068] In the above example, X １ is a group consisting of one or more selected from the group consisting of -O-, -C(=O)-, and -NR'- (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms). X １ may be —C(═O)—O— or —C(═O)—NR′—, where R′ may be independently in each occurrence a hydrogen atom or a hydrocarbon group of 1 to 3 carbon atoms.

[0069] In the above examples, q may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more. q may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, or 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0070] In the above example, Z ２ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ ２１ ３ That is. Z ２ is preferably a hydrocarbon group having 1 to 10 carbon atoms.

[0071] In the above example, Z ２ When Z is a hydrocarbon group having 1 to 10 carbon atoms, the number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more, and may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less. ２ may be a methyl group or an ethyl group, preferably a methyl group.

[0072] In the above example, Z ２１When Z is a hydrocarbon group having 1 to 10 carbon atoms, the number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more, and may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less. ２ may be a methyl group or an ethyl group, preferably a methyl group.

[0073] [Number Average Molecular Weight] The number average molecular weight of the polymer (A) is 60,000 or more and 4,000,000 or less. The number average molecular weight of the polymer (A) may be 60,000 or more, 70,000 or more, 80,000 or more, 90,000 or more, 100,000 or more, 120,000 or more, 140,000 or more, 160,000 or more, 180,000 or more, 200,000 or more, 250,000 or more, 300,000 or more, or 400,000 or more. 0 or less, 3,500,000 or less, 3,000,000 or less, 2,500,000 or less, 2,000,000 or less, 1,800,000 or less, 1,500,000 or less, 1,300,000 or less, 1,000,000 or less, 900,000 or less, 800,000 or less, 700,000 or less, 600,000 or less, 500,000 or less, or 400,000 or less. In one embodiment, the number average molecular weight of the polymer (A) may be 70,000 or more and 1,800,000 or less, preferably 70,000 or more and 700,000 or less, and more preferably 80,000 or more and 500,000 or less.

[0074] The number average molecular weight of polymer (A) can be obtained by gel permeation chromatography (polystyrene equivalent). For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (manufactured by Tosoh Corporation) was used. The column used was a combination of three TSKgel SuperMultipore HZ-M columns. An RI detector was used as the detector. Standard polystyrene (SRM706a NIST) was used as the standard substance. The analytical sample was prepared by recovering the polymer component by reprecipitation using IPA as a poor solvent, dissolving it in tetrahydrofuran to prepare a 0.1 wt% solution, and passing it through a 0.5 μm membrane filter. When measuring the number average molecular weight, the column was maintained at 40°C, tetrahydrofuran was used as the eluent, the flow rate was 0.35 mL / min, and 100 μL of the analytical sample was injected.

[0075] The number average molecular weight of the polymer (A) of the present disclosure can be controlled by a known method. For example, the number average molecular weight of the polymer (A) of the present disclosure can be controlled by adjusting the polymerization conditions when producing the polymer (A). Examples of the polymerization conditions include, but are not limited to, temperature, the type of initiator, the amount of initiator, the amount of monomer, and / or the presence or absence of a chain transfer agent.

[0076] [Composition of polymer (A)] Polymer (A) contains 90% by weight or more of repeating units derived from silicon-containing monomers based on the weight of polymer (A). The amount of repeating units derived from silicon-containing monomers may be 90% by weight or more, 91% by weight or more, 92% by weight or more, 93% by weight or more, 94% by weight or more, 95% by weight or more, 96% by weight or more, 97% by weight or more, 98% by weight or more, 99% by weight or more, or 100% by weight or less, 99% by weight or less, 98% by weight or less, 97% by weight or less, 96% by weight or less, or 95% by weight or less. Note that when the amount of repeating units derived from silicon-containing monomers is 100% by weight based on polymer (A), this means that polymer (A) is a homopolymer of the silicon-containing monomer (in other words, a homopolymer of the silicon-containing monomer).

[0077] The polymer (A) of the present disclosure may contain a monomer other than the repeating unit derived from the silicon-containing monomer. In other words, the polymer (A) of the present disclosure may be a copolymer. Such other monomer may be at least one monomer selected from the group consisting of the monomers (a) to (g) that may be contained in the vinyl polymer in the description of the compound (C) below. Detailed aspects of each of the monomers (a) to (g) are the same as those of the monomers (a) to (g) described in the description of the compound (C) below.

[0078] In one embodiment, the polymer (A) of the present disclosure may contain a repeating unit derived from a silicon-containing monomer and a repeating unit derived from a hydrocarbon group-containing monomer (a). Preferred examples of the hydrocarbon group-containing monomer (a) include the hydrocarbon group-containing monomer (a) described in the description of the compound (C) below.

[0079] The amount of repeating units derived from the other monomers may be 1% by weight or more, 2% by weight or more, 3% by weight or more, 4% by weight or more, or 5% by weight or more, and may be 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, or 1% by weight or less, based on the polymer (A). In one embodiment, the polymer (A) of the present disclosure may not contain the other monomers.

[0080] [Amount of Polymer (A)] The amount of polymer (A) in the water repellent composition may be 0.01% by weight or more, 0.03% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more, and may be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less.

[0081] The amount of polymer (A) may be 0.01 parts by weight or more, 0.03 parts by weight or more, 0.5 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, 20 parts by weight or more, or 30 parts by weight or more, relative to 100 parts by weight of the total amount of polymer (A), dispersant (B), and compound (C), and may be 95 parts by weight or less, 90 parts by weight or less, 87 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less, 65 parts by weight or less, 60 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, 5 parts by weight or less, or 3 parts by weight or less. In one embodiment, a preferred amount of polymer (A) is 8 parts by weight to 90 parts by weight, relative to 100 parts by weight of the total amount of polymer (A), dispersant (B), and compound (C).

[0082] [Polymerization Method] The polymer (A) 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, and emulsion polymerization.

[0083] In one embodiment, polymer (A) may be obtained by copolymerizing one or more of the monomers (a) to (h) exemplified as compound (C) described in detail below with a silicon-containing monomer.

[0084] Solution polymerization involves dissolving a silicon-containing monomer in an organic solvent in the presence of a polymerization initiator, purging the atmosphere with nitrogen, and then heating and stirring for 1 to 10 hours at a temperature ranging from 30 to 120°C. 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 ranging from 0.01 to 20 parts by weight, for example, from 0.01 to 10 parts by weight, per 100 parts by weight of the monomer.

[0085] The organic solvent is inert to the silicon-containing monomer and dissolves it, and may be, for example, an ester (e.g., an ester having 2 to 40 carbon atoms, specifically, ethyl acetate or butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, or methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, or isopropyl alcohol). Specific examples of organic solvents include acetone, chloroform, HCFC225, 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 silicon-containing monomer.

[0086] In emulsion polymerization, a silicon-containing monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, the mixture is heated to a predetermined temperature and stirred to polymerize.

[0087] The blending ratio of the emulsifier may be, for example, 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, 25 parts by weight or more, or 30 parts by weight or more, relative to 100 parts by weight of the total amount of the monomers, and may be 40 parts by weight or less, 30 parts by weight or less, 25 parts by weight or less, 20 parts by weight or less, 15 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0088] The blending ratio of water may be, for example, 50 parts by weight or more, 100 parts by weight or more, 150 parts by weight or more, or 200 parts by weight or more, and may be 400 parts by weight or less, 300 parts by weight or less, 250 parts by weight or less, or 200 parts by weight or less, relative to 100 parts by weight of the total amount of monomers.

[0089] The polymerization initiator may be a water-soluble one such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, or ammonium persulfate; or an oil-soluble one such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, or diisopropyl peroxydicarbonate.

[0090] The mixing ratio of the polymerization initiator may be, for example, 0.01 parts by weight or more, and 10 parts by weight or less, relative to 100 parts by weight of the monomer.

[0091] As the emulsifier, various anionic, cationic, or nonionic emulsifiers can be used, and are used in the range of 0.5 to 20 parts by weight per 100 parts by weight of the monomer. It is preferable to use an anionic and / or nonionic and / or cationic emulsifier. As the emulsifier, known emulsifiers can be used, and the dispersants exemplified as dispersants (B) described below can also be used. The emulsifiers can be used alone or in combination of two or more types.

[0092] As a method for stirring, for example, a dispersing machine such as a homomixer, an ultrasonic homogenizer, a pressure homogenizer, a milder, or a porous membrane injection dispersing machine is used, and a homomixer is preferably used. Stirring makes it easier to obtain an aqueous polymer dispersion having excellent storage stability.

[0093] Stirring conditions are appropriately set. When a homomixer is used, the rotation speed is set to, for example, 500 rpm or more and, for example, 10,000 rpm or less. The stirring time is, for example, 0.5 minutes or more and, for example, 10 minutes or less, preferably 5 minutes or less. The stirring temperature is, for example, 50°C or more and, for example, 90°C or less.

[0094] 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, to make the monomers sufficiently compatible. The addition of a compatibilizer can improve emulsifiability and copolymerizability.

[0095] 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.

[0096] 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.

[0097] In the polymerization, an organic acid may be added. For example, the organic acid may be the organic acid of the present disclosure or a carboxylic acid such as acetic acid. The organic acid may be, for example, 0.01 parts by weight or more, 0.1 parts by weight or more, or 1 part by weight or less, 0.5 parts by weight or less, relative to 100 parts by weight of the total amount of the monomers.

[0098] The polymerization conditions may be such that the heating temperature is, for example, 40° C. or higher and, for example, 80° C. or lower, and the heating time is, for example, 1 hour or higher and, for example, 6 hours or lower.

[0099] The polymer (A) can be obtained through the steps including the above. In the case of emulsion polymerization, an emulsion containing the polymer (A) and the dispersant (B) can be obtained.

[0100] [(B) Dispersant] The water repellent composition of the present disclosure contains a dispersant (B). The dispersant (B) may be at least one selected from organic dispersants and inorganic dispersants. The dispersant (B) may be at least one selected from anionic dispersants, nonionic dispersants, cationic dispersants, amphoteric dispersants, and inorganic dispersants. The water repellent composition of the present disclosure may contain a nonionic dispersant, or a combination of a nonionic dispersant and a cationic dispersant. By containing the dispersant (B), water repellency, slip resistance, and storage stability can be favorably achieved.

[0101] The dispersant (B) may be either an organic dispersant or an inorganic dispersant, or may be a combination of an organic dispersant and an inorganic dispersant.

[0102] An organic dispersant may be used as the dispersant (B). 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.

[0103] The dispersant (B) may not contain a fluorine atom.

[0104] [Nonionic Dispersant] The dispersant (B) may contain a nonionic dispersant, which may be a nonionic surfactant.

[0105] The nonionic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the nonionic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0106] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0107] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0108] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to trio-hydric (particularly di- to deca-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.

[0109] 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 trio-hydric (particularly di- to deca-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.

[0110] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamide. 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. The alkanolamine may be an alkanol 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.

[0111] 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).

[0112] 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.

[0113] 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.

[0114] 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.

[0115] The nonionic dispersant has the formula: １ O-(CH ２ CH ２ O) ｐ - (R ２ O) ｑ -R ３ [In the formula, R １ is 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), ３is 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.

[0116] R １ R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. １ Preferred specific examples of R include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. ２ Examples of the nonionic dispersant are a propylene group and a butylene group. 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.

[0117] 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. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylate, etc.

[0118] 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 contain a compound with an HLB (hydrophilic-hydrophobic balance) of 10 or less, or may be a mixture of a compound with an HLB of less than 15 (particularly 5 or less) and a compound with an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, and polyoxypropylene having an HLB value of 1 to 18, and sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

[0119] [Cationic Dispersant] The dispersant (B) may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound having no amide group.

[0120] The cationic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0121] The cationic dispersant may be aliphatic or aromatic, and examples thereof include ammonium salts (e.g., quaternary ammonium salts). The cationic dispersant may be an oxyethylene adduct ammonium salt. Specific examples include amine salt-type dispersants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines; quaternary ammonium salt-type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymer-type cationic dispersants such as Polyquaternium-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0122] The low molecular weight cationic dispersant is R ２１ -N ＋ (-R ２２ ) (-R ２３ ) (-R ２４ ) X － [In the formula, R ２１ , R ２２ , R ２３ and R ２４ is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group. ２１ , R ２２ , R ２３ and R ２４Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups) and aromatic groups (e.g., benzyl and phenyl groups). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). Examples of cationic dispersants include monoalkyltrimethylammonium salts (alkyl having 4 to 40 carbon atoms) and benzalkonium chloride.

[0123] Specifically, the low molecular weight cationic dispersant is represented by the formula: １ ｐ -N ＋ R ２ ｑ X － [In the formula, R １ is C12 or more (e.g. C １２ ~C ５０ ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group of the formula R ２ is 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), and X is a halogen atom (e.g., chlorine), or C １ ~C ４ or a fatty acid salt of 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.

[0124] Examples of low molecular weight cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, and the like.

[0125] The polymeric cationic dispersant may be any of various polymers (e.g., polyquaternium-1 to -47) having a cationic group (e.g., ammonium group, quaternary ammonium group). Examples of the polymeric cationic dispersant include cationic natural products (particularly cationic sugars) such as cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationic guar gum, cationic xanthan gum, and chitosan; and polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0126] [Anionic Dispersant] The dispersant (B) may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0127] The anionic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the anionic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0128] 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. An example of an anionic dispersant is a carboxylate (e.g., a fatty acid salt).

[0129] [Amphoteric Dispersant] The dispersant (B) may contain an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0130] The amphoteric dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the amphoteric dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0131] 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.

[0132] [Inorganic Dispersant] The dispersant (B) may contain an inorganic dispersant.

[0133] 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.

[0134] 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.

[0135] [Amount of Dispersant (B)] The amount of dispersant (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, or 100 parts by weight or more, relative to 100 parts by weight of polymer (A), 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. In one embodiment, a preferred amount of dispersant (B) is 5 to 20 parts by weight relative to 100 parts by weight of polymer (A).

[0136] The amount of dispersant (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, or 100 parts by weight or more, relative to 100 parts by weight of the total amount of polymer (A) and compound (C), 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. In one embodiment, a preferred amount of dispersant (B) is 5 to 20 parts by weight relative to 100 parts by weight of the total amount of polymer (A) and compound (C).

[0137] The amount of dispersant (B) may be 0.01 parts by weight or more, 0.03 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, or 10 parts by weight or more, relative to 100 parts by weight of the total amount of polymer (A), dispersant (B), and compound (C), and may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 15 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, or 3 parts by weight or less. In one embodiment, a preferred amount of polymer (A) is 6 parts by weight to 15 parts by weight relative to 100 parts by weight of the total amount of polymer (A), dispersant (B), and compound (C).

[0138] [Compound (C)] The water repellent composition of the present disclosure may further contain a compound (C) described below. The water repellent composition of the present disclosure preferably contains at least one compound (C) selected from the group consisting of a vinyl polymer, an isocyanate derivative, a wax, and a silicone.

[0139] In one embodiment, the water repellent composition of the present disclosure preferably contains a vinyl polymer as the compound (C).

[0140] [Vinyl Polymer] The water repellent composition of the present disclosure may further contain a vinyl polymer. The vinyl polymer is a polymer other than the polymer (A).

[0141] A vinyl polymer is a polymer obtained by polymerizing a vinyl monomer. The monomer may be any compound having a polymerizable carbon-carbon double bond (ethylenically unsaturated double bond) (>C=C<), and may be a monomer containing a vinyl group, a vinylene group, a vinylidene group, an acryloyl group, a methacryloyl group, or a derivative group thereof.

[0142] [Characteristics, etc.] The characteristics, etc. that the vinyl polymer of the present disclosure may have are shown below.

[0143] The vinyl polymer is preferably a compound containing carbon of biobased origin. The biobased content is measured in accordance with ASTM D6866. The biobased content of the vinyl polymer may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high biobased content means that the amount of fossil resource-based materials, such as petroleum, used is reduced. From this perspective, the higher the biobased content of the vinyl polymer, the more preferable it is.

[0144] The melting point of the vinyl polymer may be 30°C or higher, 40°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, and may be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower.

[0145] [Structure, etc.] The vinyl polymer in the present disclosure may not have any one 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.

[0146] The weight average molecular weight of the vinyl 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. The weight average molecular weight may be a polystyrene-equivalent molecular weight measured by GPC.

[0147] (a) Hydrocarbon Group-Containing Monomer The vinyl polymer of the present disclosure may have a repeating unit derived from a hydrocarbon group-containing monomer (a), which has one ethylenically unsaturated double bond and a hydrocarbon group having from 2 to 40 carbon atoms.

[0148] The monomer (a) preferably has a (meth)acrylic group as the group having an ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0149] (Hydrocarbon group having 2 to 40 carbon atoms) Monomer (a) has a hydrocarbon group having 2 to 40 carbon atoms. The hydrocarbon group having 2 to 40 carbon atoms may have a substituent, but preferably does not have a substituent. Here, the hydrocarbon group is a monovalent group.

[0150] 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, more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group).

[0151] The hydrocarbon group is typically monovalent and may be located at the end of the molecule, and the hydrocarbon group may have one or more methyl groups at the end. In this specification, a hydrocarbon compound (e.g., hydrocarbon wax) is understood to consist of only a monovalent hydrocarbon group and one hydrogen atom, and for example, an n-alkane having 20 carbon atoms (eicosane) is understood to consist of only an alkyl group having 20 carbon atoms and one hydrogen atom.

[0152] The number of carbon atoms in the hydrocarbon group may be 2 or more, 4 or more, 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, preferably 30 or less, 25 or less, or 20 or less.

[0153] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR' and -N(R'). ２ , —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (e.g., 1) —OR′ (particularly —OH) as a substituent (e.g., other than at the terminal).

[0154] The hydrocarbon group-containing monomer (a) is a monomer represented by the following formula: ２ = C (-R ｂ )-C(=O)-R ｃ - (R ｄ ) ｋ [In the formula, Rｂ is a hydrogen atom, a monovalent organic group or a halogen atom, R ｃ represents a divalent to tetravalent hydrocarbon group having one carbon atom (particularly, —CH ２ -, -CH(-) ２ ), -C ６ H ４ -, -O-, -S-, -C(=O)-, -S(=O) ２ - and -NR Ｃ１ - (R Ｃ１ is a group consisting of at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms, k is 1 to 3, and R ｄ are each independently a hydrocarbon group having 2 to 40 carbon atoms.]

[0155] R ｂ R 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. ｂ Examples of R are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. ｂ is preferably a hydrogen atom, a methyl group, or a chlorine atom. ｂ is particularly preferably a hydrogen atom.

[0156] R ｃ is a divalent to tetravalent group. ａ is preferably a divalent group. ｃ represents a hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ It is preferable that Y is a group constituted by at least one selected from - and -NH-. ａ is preferably not a hydrocarbon group. Examples of hydrocarbon groups having one carbon atom include -CH ２ -, -CH(-) ２ or -C(-) ３ The hydrocarbon group having one carbon atom is repeated, and -(CH ２ ) m A hydrocarbon group having two or more carbon atoms may be formed, such as Y - (where m is an integer of 1 to 5). ａmay have an NH group.

[0157] R ｃ is -R ｃ '-, -R ｃ '-R ｃ '-, -R ｃ '-C(=O)-, -C(=O)-R ｃ '-, -R ｃ '-C(=O)-R ｃ '-, -R ｃ '-R'-, -R ｃ '-R'-R ｃ '-, -R ｃ '-R'-R ｃ '-C(=O)-,-R ｃ '-R'-C(=O)-R ｃ '-, -R ｃ '-R'-R ｃ '-C(=O)-R ｃ '-, or -R ｃ '-R'-R ｃ '-R'- [wherein, R ｃ ' 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).

[0158] R ｃ 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.

[0159] R ｃ 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)—.

[0160] R ｄ are each independently a hydrocarbon group having from 2 to 40 carbon atoms, and while the above description of (hydrocarbon group having from 2 to 40 carbon atoms) is incorporated herein by reference, it 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, and especially an alkyl group. The hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 12 to 18, 16 to 26, or 15 to 26, particularly 18 to 22, or 17 to 22.

[0161] Specific examples of the monomer (a) include: (a1) a monomer represented by the formula: CH2=C(-X ａ１ )-C(=O)-Y ａ１１ -Z (-Y ａ１２ -R ａ１ ) ｎ [In the formula, R ａ１ are each independently a hydrocarbon group having 2 to 40 carbon atoms, ａ１ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ１１ is —O— or —NH—, and Y ａ１２ 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.], and (a2) a monomer represented by the formula: CH2=C(-X ａ２ )-C(=O)-Y ａ２ -R ａ２ [In the formula, R ａ２ is a hydrocarbon group having 2 to 40 carbon atoms, ａ２ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ２ is —O— or —NH—.]

[0162] (a1) Monomer The monomer (a1) is a monomer different from the monomer (a2).

[0163] The monomer (a1) may be a monomer having a hydrocarbon group having 2 to 40 carbon atoms and an NH group-containing group. The monomer (a1) may contain an amide group, a urea group, a urethane group, or a sulfonamide group. The NH group-containing group may be an amide group, a urea group, a urethane group, or a sulfonamide group. The hydrocarbon-based monomer may be a combination of a hydrocarbon-based monomer having an amide group, a urea group, a urethane group, or a sulfonamide group and a hydrocarbon-based monomer not having an amide group, a urea group, a urethane group, or a sulfonamide group. When the monomer (a1) contains such a group, the effects of the present disclosure can be effectively achieved.

[0164] The monomer (a1) is —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２ - is a (meth)acrylate or (meth)acrylamide having at least one group selected from the group consisting of:

[0165] The monomer (a1) has the formula: CH2=C(-X ａ１ )-C(=O)-Y ａ１１ -Z (-Y ａ１２ -R ａ１ ) ｎ [In the formula, R ａ１ are each independently a hydrocarbon group having 2 to 40 carbon atoms, ａ１ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ１１ is —O— or —NH—, and Y ａ１２ 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. ａ１２ and / or Z may not be a direct bond. ａ１２ and Z may not be a direct bond at the same time.

[0166] 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 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22 carbon atoms.

[0167] 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.

[0168] Y ａ１２represents -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.

[0169] Y ａ１２ Specific examples include direct bond, -O-, -NH-, -OC(=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 -, -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 ), 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 - [where m is an integer from 1 to 5.]

[0170] In particular, Y ａ１２ may have an NH group.

[0171] Y ａ１２ is -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 H４ - is preferred. ａ１２ is more preferably —NH—C(═O)—, —C(═O)—NH—, —O—C(═O)—NH—, —NH—C(═O)—O— or —NH—C(═O)—NH—. ａ１２ may not be a direct bond.

[0172] 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-)CH ２ -, -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.

[0173] Monomer (a1) is CH2=C(-X ａ１ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R ａ１ , C.H. ２ =C(-X ａ１)-C(=O)-O-(CH ２ ) ｍ -OC(=O)-NH-R ａ１ , C.H. ２ =C(-X ａ１ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-OR ａ１ , C.H. ２ =C(-X ａ１ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-NH-R ａ１ Preferably, R ａ１ and X ａ１ has the same meaning as above.]. The monomer (a1) is CH2=C(-X ａ１ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R ａ１ It is particularly preferred that:

[0174] Monomer (a1) 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 (a1) can be produced by reacting a (meth)acrylate having an isocyanate group in its 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.

[0175] 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;

[0176]

[0177]

[0178]

[0179]

[0180]

[0181] [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 methacrylic compound having a methyl group at the α-position and an α-chloroacrylic compound having a chlorine atom at the α-position.

[0182] The monomer (a1) has the formula: ａ１２ -C(=O)-NH-R ａ１３ -O-R ａ１１ [In the formula, R ａ１１ represents an organic residue having an ethylenically unsaturated polymerizable group, R ａ１２ is a hydrocarbon group having 2 to 40 carbon atoms, R ａ１３ is a hydrocarbon group having 1 to 5 carbon atoms.]

[0183] R ａ１１ is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a polymer carbon-carbon double bond. ａ１１１ =CH ２ , -CHR ａ１１１ =CH ２ , -CH ２ CHR ａ１１１ =CH ２ and the like. ａ１１１is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ａ１１ 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. ａ１１ is -C(=O)CR ａ１１１ =CH ２ It is preferable that:

[0184] R ａ１２ is the same as the hydrocarbon group contained in the monomer (a) described above, and is a hydrocarbon group having from 2 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. ａ１２ The number of carbon atoms is 6 or more and 40 or less, preferably 11 to 27, and particularly preferably 15 to 23.

[0185] R ａ１３ 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. ａ１３ The number of carbon atoms in R is preferably 2 to 4, and particularly preferably 2. ａ１３ is preferably an alkylene group.

[0186] The amide group-containing monomer is R ａ１２ is one type (for example, R ａ１２ is only a compound having 17 carbon atoms), or R ａ１２ A combination of multiple ａ１２ a compound having 17 carbon atoms, and R ａ１２ and a compound having 15 carbon atoms.

[0187] 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.

[0188] 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 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.

[0189] (a2) Monomer Monomer (a2) has the formula: CH2=C(-X ａ２ )-C(=O)-Y ａ２ -R ａ２ [In the formula, R ａ２ is a hydrocarbon group having 2 to 40 carbon atoms, ａ２ is a hydrogen atom, a monovalent organic group or a halogen atom,ａ２ is —O— or —NH—.]

[0190] The monomer (a2) is Y ａ２ a long chain acrylate ester monomer in which Y is —O—; ａ２ is a long chain acrylamide monomer in which R is —NH—. ａ２ is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. ａ２ In the formula (I), the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example, 16 to 26, and particularly preferably 18 to 22. 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.

[0191] 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.

[0192] The vinyl polymers of the present disclosure may include repeat units derived from the following monomers:

[0193] (b) Hydrophilic Group-Containing Monomer The vinyl polymer of the present disclosure may contain a repeating unit derived from a hydrophilic group-containing monomer (b). The monomer (b) is a monomer other than the monomer (a) that has a hydrophilic group.

[0194] The monomer (b) preferably has a (meth)acrylic group as the group having an ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond. The monomer (a) may have one or two groups having an ethylenically unsaturated double bond, but preferably has only one.

[0195] The hydrophilic group is preferably an oxyalkylene-containing group (the alkylene group has 2 to 6 carbon atoms), and particularly preferably an oxyethylene group. In particular, the monomer (b) 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.

[0196] Monomer (b) has the formula: CH ２ =CX ｂ C(=O)-Y ｂ - (R ｂ O) ｎ -A ｂ [In the formula, X ｂ is a hydrogen atom or a methyl group, and Y ｂ is —O— or —NH—, R ｂ are each independently an alkylene group having 2 to 6 carbon atoms, ｂ represents a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH ２ =CX ｂ C(═O)—, and n is an integer of 1 to 90.

[0197] Examples of monomer (b) are those of the formula: CH ２ =CX ｂ C(=O)-O-(R ｂ O) ｎ -A ｂｉ (b1) and CH ２ =CX ｂ C(=O)-O-(R ｂ O) ｎ -C(=O)CX ｂ =CH ２ (b2), CH ２ =CX ｂ C(=O)-NH-(R ｂ O) ｎ -A ｂｉ (b3) wherein Xｂ are each independently a hydrogen atom or a methyl group; ｂｉ are each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, ｂ are each independently an alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 to 90.

[0198] n may be, for example, 1 to 50, particularly 1 to 30, and especially 1 to 15 or 2 to 15. Alternatively, n may be, for example, 1. R ｂ 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. ｂ O) n In -, R may be two or more types (for example, two to four types, particularly two types), and -(R ｂ 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.

[0199] R in formulas (b1), (b2) and (b3) ｂ is particularly preferably an ethylene group, a propylene group or a butylene group, and particularly preferably a butylene group. ｂR 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. ｂ 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 (b) may be a mixture of two or more types. In this case, at least one of the monomers (b) is a mixture of R in formula (b1), (b2), or (b3). ｂ is preferably an ethylene group, a propylene group, or a butylene group. When a polyalkylene glycol di(meth)acrylate represented by formula (b2) is used, it is not preferable to use it alone as the monomer (b), but it is preferable to use it in combination with the monomer (b1). In that case, it is also preferable to keep the content of the compound represented by formula (b2) to less than 30% by weight of the monomer (b) used.

[0200] Specific examples of the monomer (b) include, but are not limited to, the following: CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)OH CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H CH2=CHCOO-CH2CH2CH(CH3)OH CH2=CHCOO-CH2CH(CH3)CH2O-H CH2=CHCOO-CH(CH3)CH2CH2O-H CH2=CHCOO-CH2CH(CH2CH3)OH CH2=CHCOO-CH2C(CH3)2O-H CH2=CHCOO-CH(CH2CH3)CH2O-H CH2=CHCOO-C(CH3)2CH2O-H CH2=CHCOO-CH(CH3)CH(CH3)OH CH2=CHCOO-C(CH3)(CH2CH3)OH CH2=CHCOO-(CH2CH2O)2-H CH2=CHCOO-(CH2CH2O)4-H CH2=CHCOO-(CH2CH2O)5-H CH2=CHCOO-(CH2CH2O)6-H CH2=CHCOO-(CH2CH2O)5-CH3 CH2=CHCOO-(CH2CH2O)9-CH3 CH2=CHCOO-(CH2CH2O)23 -CH3 CH2=CHCOO-(CH2CH2O) 90 -CH3

[0201] CH2=CHCOO-(CH2CH(CH3)O)9-H CH2=CHCOO-(CH2CH(CH3)O)9-CH3 CH2=CHCOO-(CH2CH(CH3)O) 12 -CH3 CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=CHCOO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=CHCOO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0202] CH2=CHCOO-(CH2CH2O)9-H CH2=C(CH3)COO-CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH3)O-H CH2=C(CH3)COO-CH(CH3)CH2O-H CH2=C(CH3)COO-CH2CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH(CH3)O-H CH2=C(CH3)COO-CH2CH(CH3)CH2O-H CH2=C(CH3)COO-CH(CH3)CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH2CH3)O-H CH2=C(CH3)COO-CH2C(CH3)2O-H CH2=C(CH3)COO-CH(CH2CH3)CH2O-H CH2=C(CH3)COO-C(CH3)2CH2O-H CH2=C(CH3)COO-CH(CH3)CH(CH3)O-H CH2=C(CH3)COO-C(CH3)(CH2CH3)O-H CH2=C(CH3)COO-(CH2CH2O)2-H CH2=C(CH3)COO-(CH2CH2O)4-H CH2=C(CH3)COO-(CH2CH2O)5-H CH2=C(CH3)COO-(CH2CH2O)6-H CH2=C(CH3)COO-(CH2CH2O)9-H CH2=C(CH3)COO-(CH2CH2O)5-CH3 CH2=C(CH3)COO-(CH2CH2O)9-CH3 CH2=C(CH3)COO-(CH2CH2O) 23 -CH3 CH2=C(CH3)COO-(CH2CH2O) 90 -CH3 CH2=C(CH3)COO-(CH2CH(CH3)O)9-H

[0203] CH2=C(CH3)COO-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)COO-(CH2CH(CH3)O) 12-CH3 CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=C(CH3)COO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=C(CH3)COO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0204] CH2=CH-C(=O)-NH-CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH3)OH CH2=CH-C(=O)-NH-CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH(CH3)OH CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH2CH3)OH CH2=CH-C(=O)-NH-CH2C(CH3)2O-H CH2=CH-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=CH-C(=O)-NH-C(CH3)2CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=CH-C(=O)-NH-(CH2CH2O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)4-H CH2=CH-C(=O)-NH-(CH2CH2O)5-H CH2=CH-C(=O)-NH-(CH2CH2O)6-H CH2=CH-C(=O)-NH-(CH2CH2O)9-H CH2=CH-C(=O)-NH-(CH2CH2O)5-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 23-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 90 -CH3

[0205] CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3 CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0206] CH2=C(CH3)-C(=O)-NH-CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-CH2C(CH3)2O-H CH2=C(CH3)-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-C(CH3)2CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-(CH2CH2O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)4-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 90 -CH3

[0207] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O) 12-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0208] The monomer (b) may be X ２ is a hydrogen atom. The monomer (b) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

[0209] (c) Ionic Group-Containing Monomer The vinyl polymer of the present disclosure may contain a repeating unit derived from an ionic group-containing monomer (c). The monomer (c) is preferably a monomer (particularly, an acrylic monomer) containing one ethylenically unsaturated double bond and an ionic group. The ionic group is an anionic group and / or a cationic group, or a salt thereof.

[0210] The monomer (c) 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.

[0211] Examples of the monomer having an anionic group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Specific examples of the monomer having an anionic 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.

[0212] Examples of salts of anionic groups include alkali metal salts, alkaline earth metal salts, and ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0213] In the monomer having a cationic group, examples of the cationic 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 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 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 an ethylenically unsaturated double bond. The cationic group may be in the form of a salt.

[0214] The cationic 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.

[0215] Specific examples of the monomer having a cationic group are as follows: CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetate) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br - CH2=C(CH3)COO-CH2CH2-N + (CH3)3I - CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3 CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0216] The ionic group-containing monomer (c) is preferably methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate, and more preferably methacrylic acid or dimethylaminoethyl methacrylate.

[0217] (d) Halogenated Olefin Monomer The vinyl polymer of the present disclosure may have a repeating unit derived from a halogenated olefin monomer (d). The halogenated olefin monomer (d) may not contain a fluorine atom. The halogenated olefin monomer (d) is preferably an olefin having 2 to 20 carbon atoms and substituted with 1 to 10 chlorine atoms, bromine atoms, or iodine atoms. The halogenated olefin monomer (d) 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 (d) include vinyl halides such as vinyl chloride, vinyl bromide, 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 the durability of water repellency). The presence of repeat units derived from the halogenated olefin monomer (d) can enhance the washing durability of the vinyl polymer.

[0218] (e) Crosslinkable Monomer The vinyl polymer of the present disclosure may contain a repeating unit derived from a crosslinkable monomer (e). The crosslinkable monomer (e) has a reactive group and / or an ethylenically unsaturated double bond (preferably, a (meth)acrylate group). The crosslinkable monomer (e) may be a monomer that does not contain a fluorine atom. The crosslinkable monomer (e) may be a compound having at least two ethylenically unsaturated double bonds (preferably, a (meth)acrylate group), or a compound having 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.

[0219] Examples of the crosslinkable monomer may be a vinyl monomer having a reactive group, a mono(meth)acrylate, a di(meth)acrylate or a di(meth)acrylamide having a reactive group.

[0220] Examples of crosslinkable monomers include, but are not limited to, diacetone (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (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.

[0221] (f) Cyclic hydrocarbon group-containing monomer The vinyl polymer of the present disclosure may have a repeating unit derived from a cyclic hydrocarbon group-containing monomer (f). The cyclic hydrocarbon group-containing monomer (f) is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group. The vinyl polymer of the present disclosure may be a styrene polymer having a repeating unit derived from styrene or a styrene derivative.

[0222] The cyclic hydrocarbon group-containing monomer (f) 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.

[0223] The cyclic hydrocarbon group may be alicyclic or aromatic. The cyclic hydrocarbon group may be saturated or unsaturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, with a bridged ring group being preferred. The cyclic hydrocarbon group may have a chain group (e.g., a halogen atom, a linear or branched chain hydrocarbon group (particularly a linear or branched chain hydrocarbon group having 1 to 20 carbon atoms)).

[0224] 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.

[0225] 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.

[0226] Specific examples of the cyclic hydrocarbon group-containing monomer (f) 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.

[0227] An example of the cyclic hydrocarbon group-containing monomer (f) is a styrene compound. The styrene compound may be modified with a chain group (for example, a halogen atom, or a linear or branched hydrocarbon group (particularly a linear or branched hydrocarbon group having 1 to 20 carbon atoms). Specific examples thereof include styrene, 4-t-butylstyrene, 3,5-di-t-butylstyrene, 2,4,6-tri-t-butylstyrene, 4-methylstyrene, 3,5-dimethylstyrene, and 2,4,6-trimethylstyrene. The styrene compound may be an α-methylstyrene compound or an α-chlorostyrene compound in which the α-position is a chlorine atom, or may be a styrene compound in which the α-position is a hydrogen atom.

[0228] (g) Other Monomers The other monomers are not limited to these examples and include acrylonitrile, short-chain alkyl (meth)acrylate, vinyl acetate, vinyl alkyl ether, etc. The other monomers (h) may be used alone or in combination of two or more.

[0229] [Polymer Composition] The vinyl polymer of the present disclosure may be a polymer of one type selected from the group consisting of monomers (a) to (g), or may be a copolymer of two or more types. The combination of monomers (a) to (g) constituting the repeating units of the vinyl polymer of the present disclosure is not particularly limited, and examples are as follows (parentheses omitted): a a+b a+b+c a+c a+d a+b+c+d a+b+c+d+e a+b+c+d+e+f In the above combinations, monomer (g) may be used in place of or in addition to monomer (a). Another monomer (g) may also be used in the above combination. For pulp products, it is preferable to use monomer (a), monomer (b), and monomer (c) in combination.

[0230] 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, 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 vinyl polymer.

[0231] The amount of the monomer (a) (particularly the monomer (a1)) may be more than 90% by weight, 92% by weight or more, 94% by weight or more, 96% by weight or more, 98% by weight or more, 99% by weight or more, 99.5% by weight or more, or 100% by weight, based on the vinyl polymer, for example, 93% by weight or more, preferably more than 97% by weight, and 100% by weight or less, 99% by weight or less, 97% by weight or less, 95% by weight or less, or 93% by weight or less, and in one embodiment, more than 90% by weight and 100% by weight or less. The amount of the monomer (a1) may be 100% by weight based on the vinyl polymer.

[0232] In the monomer (a), the amount of the monomer (a1) 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, preferably 30% by weight or more, and may be 100% by weight or less, 90% by weight or less, 80% by weight or less, 50% by weight or less, or 30% by weight or less.

[0233] 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 may be 100% by weight or less, 90% by weight or less, 80% by weight or less, 50% by weight or less, or 30% by weight or less.

[0234] 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 vinyl 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).

[0235] 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 vinyl 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).

[0236] 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, based on the vinyl polymer; and the amount of repeating units derived from monomer (d) 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 vinyl 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).

[0237] 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 vinyl 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).

[0238] 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 vinyl 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).

[0239] 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 vinyl 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).

[0240] 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 vinyl 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).

[0241] When the monomer (g) is used instead of the monomer (a), "100 parts by weight of the amount of repeating units derived from the monomer (a)" in the above description of the amount of each monomer may be read as "100 parts by weight of the amount of repeating units derived from the monomer (g)."

[0242] [Polymerization Method] Vinyl polymers can be produced by known polymerization methods, and the polymerization reaction conditions can be selected arbitrarily. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0243] 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.

[0244] 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 or butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, or methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, or isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCFC225, 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.

[0245] 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.

[0246] 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.

[0247] 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.

[0248] 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.

[0249] [Isocyanate Derivative] The water repellent composition of the present disclosure may contain an isocyanate derivative, and preferably may contain an isocyanate derivative obtained by reacting an active hydrogen compound with a raw material isocyanate, which will be described below.

[0250] 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.

[0251] The isocyanate derivative has -NHCO- formed by the reaction of an active hydrogen compound with a raw material isocyanate (here, -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 compound (a) with an active hydrogen-reactive group (typically an isocyanate group) of compound (b). The isocyanate derivative is typically a urethane (particularly a polyurethane).

[0252] The isocyanate derivative may have a hydrocarbon group having 6 to 40 carbon atoms. The hydrocarbon group 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. The number of carbon atoms in the hydrocarbon group 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.

[0253] The isocyanate derivative may have an alkyl group having 12 to 30 carbon atoms. The alkyl group having 12 to 30 carbon atoms may be branched or linear, more preferably chain-like, and particularly linear. The alkyl group contained in the isocyanate derivative may be 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 12 or more or 16 or more. The alkyl group contained in the isocyanate derivative may be 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.

[0254] 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. The weight average molecular weight of the isocyanate derivative 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.

[0255] 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. The water contact angle of the isocyanate derivative 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 onto the spin-coated film and measuring the contact angle 1 second after the drop has landed.

[0256] [Active Hydrogen Compound] The active hydrogen compound contains an active hydrogen group that reacts with an isocyanate group.

[0257] 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.

[0258] [(α1) Hydrocarbon Alcohol] The active hydrogen compound may be a hydrocarbon alcohol (α1) composed of a hydrocarbon group and a hydroxyl group.

[0259] The hydrocarbon group in the hydrocarbon alcohol (α1) may be the above-mentioned hydrocarbon group having from 6 to 40 carbon atoms, and the above description is incorporated herein. The hydrocarbon group in the hydrocarbon alcohol (α1) may preferably be the above-mentioned alkyl group having from 12 to 30 carbon atoms, and the above description is incorporated herein.

[0260] The hydrocarbon alcohol (α1) preferably has one hydroxy group per molecule.

[0261] Examples of the hydrocarbon alcohol (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.

[0262] 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 weight or more, preferably 55 parts by weight or more, more preferably 70 parts by weight or more, and for example, 90 parts by weight or less, preferably 80 parts by weight or less, relative to 100 parts by weight of the total amount 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 weight or more, preferably 20 parts by weight or more, and for example, 60 parts by weight or less, preferably 45 parts by weight or less, more preferably 30 parts by weight or less, relative to 100 parts by weight of the total amount 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.

[0263] [(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 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.

[0264] The number of hydrocarbon groups having from 6 to 40 carbon atoms in the sugar alcohol / hydroxy acid modified compound (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 compound (α2) may be 12 or less, 9 or less, 6 or less, or 3 or less. The hydrocarbon groups in the sugar alcohol / hydroxy acid modified compound (α2) may be the hydrocarbon groups having from 6 to 40 carbon atoms described above, and the above explanation is incorporated herein. The sugar alcohol / hydroxy acid modified compound (α2) may have an alkyl group having from 12 to 30 carbon atoms. The above explanation is incorporated herein for the alkyl group having from 12 to 30 carbon atoms.

[0265] 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 the sugar alcohol / hydroxy acid modified compound, 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-. The carbon atom having from 6 to 40 carbon atoms in sugar alcohol / hydroxy acid modified compound (α2) may preferably be the above-mentioned alkyl group having from 12 to 30 carbon atoms, and the above explanation is incorporated herein by reference.

[0266] ((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)R α２ 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 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. The hydrocarbon group in the sorbitan modified product (α21) may be the above-mentioned hydrocarbon group having 6 to 40 carbon atoms, and the above explanation is incorporated herein by reference. The sorbitan modified product (α21) may have an alkyl group having 12 to 30 carbon atoms. The above explanation is incorporated herein by reference for the alkyl group having 12 to 30 carbon atoms. Commercially available sorbitans such as SPAN can be used as the alkyl sorbitan.

[0267] 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.

[0268] In one embodiment, R α２may 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.

[0269] 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 α２is 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.

[0270] ((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 an alkyl group. The hydrocarbon group in the citric acid modification (α22) may be the above-mentioned hydrocarbon group having from 6 to 40 carbon atoms, and the above explanation is incorporated herein. The citric acid modification (α22) may have an alkyl group having from 12 to 30 carbon atoms. The above explanation is incorporated herein for the alkyl group having from 12 to 30 carbon atoms. A mixture of citrates having various values ​​of active hydrogen substituents may also be used, and the R α２ 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.

[0271] ((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 pentaerythritol modified product (α23) may contain a mixture of a compound having 6 to 40 carbon atoms and a compound having 12 to 30 carbon atoms. The hydrocarbon group in the pentaerythritol modified product (α23) may be the hydrocarbon group having 6 to 40 carbon atoms as described above, and the above explanation is incorporated herein by reference. The pentaerythritol modified product (α23) may have an alkyl group having 12 to 30 carbon atoms. The above explanation is incorporated herein by reference for the alkyl group having 12 to 30 carbon atoms.

[0272] [(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.

[0273] The cationic active hydrogen compound (α3) preferably has two or more hydroxy groups per molecule.

[0274] An example of the cationic group is a tertiary amino group.

[0275] 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.

[0276] 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.

[0277] 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.

[0278] 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.

[0279] The cationic active hydrogen compound (or the portion of the polymer derived from the cationic active hydrogen compound) may form a salt with an acid compound.

[0280] 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 (α) may contain other active hydrogen compounds (α4).

[0281] ((α41) Compound) The active hydrogen compound (α4) is represented by the formula R α４１ -X α４１ [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 30Straight 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 α４１４ is 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.

[0282] 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) tThe -(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.

[0283] 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-C 30 Straight or branched alkyl, amine functional C1-C 30 It is selected from straight or branched chain alkyl.

[0284] 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 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 4 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 α４１２ Polyether 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.

[0285] 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 30hydroxy-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.

[0286] 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 30 and the like. The alkyl groups include, but are not limited to, straight or branched chain alkyl groups.

[0287] 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 α４１is HO-S(O)2R α４１４ -), but are not limited to.

[0288] (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.

[0289] 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.

[0290] ((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.

[0291] In one embodiment, the active hydrogen compound may be at least one selected from the group consisting of hydrocarbon alcohols, modified sugar alcohols, and modified hydroxy acids.

[0292] Starting Isocyanate The isocyanate derivative has a moiety derived from the starting isocyanate.

[0293] The starting isocyanate may be an aromatic polyisocyanate, an acyclic aliphatic polyisocyanate, a cyclic alicyclic polyisocyanate, or a bridged cyclic alicyclic polyisocyanate.

[0294] The aromatic polyisocyanate is a compound having an aromatic ring and an isocyanate group. The aromatic polyisocyanate may have one or more, two or more, or three or more aromatic rings, and may have five or fewer, four or fewer, or three or fewer aromatic rings.

[0295] The acyclic aliphatic polyisocyanate is an aliphatic polyisocyanate that does not have a ring structure. The acyclic aliphatic polyisocyanate may have an aliphatic hydrocarbon group having from 2 to 20 carbon atoms. The aliphatic hydrocarbon group having from 2 to 20 carbon atoms may be a divalent aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group may be 2 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, or 14 or more, preferably 4 or more, 6 or more, or 8 or more. The number of carbon atoms in the aliphatic hydrocarbon group may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, or 10 or less, preferably 14 or less, 12 or less, or 10 or less. In one aspect, the acyclic aliphatic polyisocyanate may be a polyisocyanate compound having an isocyanate group at the terminal of an alkylene group.

[0296] The cyclic alicyclic polyisocyanate is an aliphatic polyisocyanate having a ring structure. The cyclic alicyclic polyisocyanate has a carbon ring that is not an aromatic ring. The cyclic alicyclic polyisocyanate may have an aliphatic hydrocarbon group having from 2 to 20 carbon atoms. The aliphatic hydrocarbon group having from 2 to 20 carbon atoms is described above in relation to the acyclic aliphatic polyisocyanate.

[0297] The bridged alicyclic polyisocyanate is a polycyclic compound having a crosslinked structure with a methylene group or the like in the ring structure. The bridged alicyclic polyisocyanate may have an aliphatic hydrocarbon group having from 2 to 20 carbon atoms. The aliphatic hydrocarbon group having from 2 to 20 carbon atoms is the same as that described above for the acyclic aliphatic polyisocyanate.

[0298] The raw material isocyanate may be a derivative of the raw material isocyanate, such as an isocyanurate derivative, an allophanate derivative, a polyol derivative, a biuret derivative, a urea derivative, an oxadiazinetrione derivative, a carbodiimide derivative, a uretdione derivative, or a uretonimine derivative.

[0299] The starting isocyanate may be a derivative of a polyisocyanate selected from the group consisting of aromatic polyisocyanates, acyclic aliphatic polyisocyanates, cyclic alicyclic polyisocyanates, and bridged cyclic alicyclic polyisocyanates.

[0300] In one aspect, the starting isocyanate may be an isocyanurate derivative or a biuret derivative.

[0301] In one aspect, the starting isocyanate may be an acyclic aliphatic polyisocyanate.

[0302] 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), methylcyclohexa Cycloalicyclic polyisocyanates selected from diisocyanates (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 norbornene diisocyanate, norbornane diisocyanatomethyl, bicycloheptane triisocyanate, diisocyanatomethyl bicycloheptane, and di(diisocyanatomethyl)tricyclodecane; and biuret-modified products of the above 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 reacting the above-mentioned polyisocyanates with monohydric alcohols or dihydric alcohols, etc.), polyol derivatives (for example, polyol derivatives (alcohol adducts, preferably trimethylolpropane adducts) produced by reacting the above-mentioned polyisocyanates with trihydric alcohols (for example, trimethylolpropane, etc.)), biuret derivatives (for example, biuret derivatives produced by reacting the above-mentioned polyisocyanates with water or amines, etc.), urea derivatives (for example, urea derivatives produced by reacting the above-mentioned polyisocyanates with diamines, etc.), Examples of the oxadiazinetrione derivatives include oxadiazinetrione derivatives (such as the oxadiazinetrione produced by the reaction of the above-mentioned polyisocyanate with carbon dioxide gas), carbodiimide derivatives (such as the carbodiimide derivatives produced by the above-mentioned decarboxylation condensation reaction of polyisocyanate), uretdione derivatives, and uretonimine derivatives.

[0303] 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.

[0304] [Method for synthesizing isocyanate derivatives]

[0305] 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.

[0306] [Composition of Isocyanate Derivative] The amount of the portion derived from compound (α) 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, based on the isocyanate derivative. The amount of the portion derived from monomer (α) 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.

[0307] 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, relative to the portion derived from the active hydrogen compound. The amount of the portion derived from the hydrocarbon alcohol (α1) 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, relative to the portion derived from the active hydrogen compound.

[0308] The amount of the sugar alcohol / hydroxy acid modified product (α2) derived moiety 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 amount of the active hydrogen compound derived moiety. The amount of the sugar alcohol / hydroxy acid modified product (α2) derived moiety 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 relative to the amount of the active hydrogen compound derived moiety.

[0309] 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, based on the portion derived from the active hydrogen compound. The amount of the portion derived from the cationic active hydrogen compound (α3) 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.

[0310] The amount of the portion derived from the other active hydrogen-containing compound (α4) may be 10 wt% or more, 20 wt% or more, 30 wt% or more, 40 wt% or more, 50 wt% or more, 60 wt% or more, or 70 wt% or more relative to the portion derived from the other active hydrogen-containing compound (α4). The amount of the portion derived from the other active hydrogen-containing compound (α4) may be 75 wt% or less, 65 wt% or less, 55 wt% or less, 45 wt% or less, 35 wt% or less, 25 wt% or less, or 15 wt% or less relative to the portion derived from the active hydrogen compound.

[0311] The amount of the portion derived from the starting 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, based on the isocyanate derivative. The amount of the portion derived from the starting isocyanate 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.

[0312] [Amount of Isocyanate Derivative] The amount of the isocyanate derivative 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, or 20 parts by weight or more per 100 parts by weight of the polymer (A). The amount of the isocyanate derivative may be 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 per 100 parts by weight of the polymer (A).

[0313] [Wax] The water repellent composition of the present disclosure preferably contains a wax in addition to the vinyl polymer, particularly the hydrocarbon group-containing monomer (a). By containing a wax, it is possible to achieve both water repellency and slip resistance. The water repellent composition of the present disclosure may contain both a silicone and a wax, or may contain only one of a silicone and a wax.

[0314] The HD (n-hexadecane) contact angle of the wax may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may be 100° or less, 90° or less, or 75° or less. When the wax has an HD contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly oil repellency) to the substrate. The HD contact angle is the static contact angle of the wax with respect to a spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle one second after the drop lands.

[0315] The water contact angle of the wax may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 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 wax has a water contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. The water contact angle is the static contact angle of the wax 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.

[0316] The wax may be a low molecular weight (e.g., a molecular weight of 1000 or less, or 500 or less) or a polymer. When the wax is a polymer, its weight average molecular weight may be 1000 or more, 3000 or more, 5000 or more, 7500 or more, 10000 or more, 30000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, or 10,000,000 or less, 7,500,000 or less, 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, 3 ...,000 or less, 75000 or less, 50000 or less, or 3,000 or less.

[0317] The melting point of the wax may be 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, particularly preferably 55°C or higher, and may be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower, preferably 120°C or lower. The melting point of the wax may be measured in accordance with JIS K 2235-1991. The melting point usually corresponds to the peak top temperature of the endothermic peak with the maximum temperature before melting observed in DSC (differential scanning calorimetry).

[0318] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, animal and vegetable wax, and mineral wax. 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-eicosene, 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 compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500, or 300 to 1000. These may be used alone or in combination of two or more.

[0319] The melting point of the wax may be 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.

[0320] [Types of Wax, etc.] Examples of waxes include mineral waxes (petroleum waxes) such as paraffin wax, microcrystalline wax, montan wax, ozokerite wax, ceresin wax, and petrolatum wax; and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, and polypropylene wax, and are preferably paraffin wax or microcrystalline wax. The wax in the present disclosure may be a hydrocarbon wax, preferably a chain aliphatic hydrocarbon, for example, a linear or branched hydrocarbon, and particularly a linear hydrocarbon.

[0321] [Silicone] The water repellent composition of the present disclosure may contain silicone.

[0322] Silicones have the formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 ) ２ -O-] ｂ -Si(R 53 ) 3　　 (S1) [wherein, R ５１ each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or an alkoxy group having 1 to 40 carbon atoms; ５３ each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a saturated hydrocarbon group having 1 to 40 carbon atoms, a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 5 to 200.

[0323] R ５１ and R ５３ In the formula (R), the alkyl group having 1 to 40 carbon atoms and the aryl group having 6 to 40 carbon atoms may be unsubstituted or substituted. ５１ and R ５３ Specific examples of R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group; a cyclopentyl group, a cyclohexyl group, a cycloheptyl group; a phenyl group, a tolyl group, a naphthyl group, or a group in which some or all of the hydrogen atoms bonded to these groups have been substituted with a halogen atom, an amino group, a cyano group, or the like. ５１ and R ５３ is preferably a methyl group or an ethyl group. ５１ and R ５３ In the formula (I), the alkoxy group having 1 to 40 carbon atoms may be linear or branched. Examples of the alkoxy group having 1 to 40 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0324] The silicone may have at least one long-chain hydrocarbon group. For example, R ５１ At least one of R ５３ or R ５１ and R ５３ At least one of each of R ５１ At least one (for example, one) of the above may be a long-chain hydrocarbon group. Here, the long-chain hydrocarbon group may be a saturated hydrocarbon group having 6 or more, 10 or more, 15 or more, or 20 or more carbon atoms, preferably 10 or more or 23 or more carbon atoms. Here, the hydrocarbon group may be linear or branched, and is preferably an alkyl group. Specific examples of hydrocarbon groups include a hexyl group (6 carbon atoms), an octyl group (8 carbon atoms), a lauryl group (12 carbon atoms), a myristyl group (14 carbon atoms), a stearyl group (18 carbon atoms), a behenyl group (22 carbon atoms), a tricosyl group (23 carbon atoms), a lignoceryl group (tetracosyl group, 24 carbon atoms), a cellotyl group (hexacosyl group, 26 carbon atoms), a monthyl group (octacosyl group, 28 carbon atoms), a melissyl group (triacontane group, 30 carbon atoms), and a dotriacontane group (32 carbon atoms).

[0325] The long-chain hydrocarbon group R is preferred because it is easy to produce industrially and is readily available. ５１ and R ５３ Other than R ５１ and R ５３ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0326] a is an integer of 0 or more. In terms of ease of industrial production and availability, a may be 40 or less, 30 or less, or 20 or less, and is preferably 30 or less.

[0327] The sum of a and b is 5 to 200. From the viewpoints of ease of industrial production, availability, and handling, the sum of a and b is preferably 10 to 100, and more preferably 40 to 60. a may be 0 to 150, for example, 1 to 100. The lower limit of b may be 1, 2, or 3, and the upper limit of b may be 150, 10, or 5.

[0328] When a or b is 2 or more, a plurality of R ５１ and R ５２ may be the same or different.

[0329] R ５１ and R ５３ group (for example, when represented by the following formula (S2), R ５１ and R ５２ Group and R ５３ It is preferred that 50 mol % or more of the total of the alkyl groups) be methyl groups.

[0330] The order of the repeating units bound by a or b is not limited to the order shown in the chemical formula, and can be any order. That is, the silicone may be a random polymer or a block polymer.

[0331] For example, silicones may be of the formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )(R 52 )-O-] ｂ -Si(R 53 ) 3　　 (S2) [wherein, R ５１ each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a long-chain hydrocarbon group; ５２ each independently represents a long chain hydrocarbon group; ５３ each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a long-chain hydrocarbon group, a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 5 to 200. In formula (S2), R ５１ and R ５３ may have an alkyl group having 3 to 40 carbon atoms or an unsaturated hydrocarbon group having 6 to 40 carbon atoms (for example, a hydrocarbon group having an aromatic ring), but it is preferable that it does not have these groups.

[0332] Examples of silicones are: [In the formula, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a+b) is an integer of 5 to 200, and n is an integer of 1 to 36 (preferably n is the number of carbon atoms in the long-chain hydrocarbon group).]

[0333] Silicone can be synthesized by a conventionally known method, for example, by subjecting silicone having a SiH group to a hydrosilylation reaction with an α-olefin.

[0334] Examples of silicones containing SiH groups include methylhydrogensilicones with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methylhydrogensiloxane. Among these, methylhydrogensilicones are preferred due to their ease of industrial production and availability. Hydrogensilicones (e.g., methylhydrogensilicones) are polydiorganosiloxanes in which a portion of the side chain is substituted with hydrogen, with the hydrogen atoms directly bonded to silicon atoms. When using hydrogensilicones, a catalyst may be used to improve reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine-based catalysts can be used. Metal salts of organic acids are preferred as catalysts, and fatty acids are preferred as organic acids. Zinc stearate, for example, can be used. The catalyst is preferably used in an amount of 10 to 40% relative to the methylhydrogensilicone, as this enhances its effectiveness. Two or more of amino-modified silicones, epoxy-modified silicones, carboxy-modified silicones, and methylhydrogensilicones may be mixed. All of these silicones have reactive groups, and it is preferable that they have film-forming properties. The term "film-forming ability" refers to the ability of the silicone to form a solid film, rather than an oil or gel film, after being attached to the surface of a fiber in an emulsion state.

[0335] α-olefins are compounds from which long-chain hydrocarbon groups in silicones are derived. Specific examples of α-olefins are 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triacontene, and 1-dotriacontene. The hydrosilylation reaction may be carried out by reacting the α-olefin with the above-mentioned silicone having SiH groups in the presence of a catalyst, either stepwise or all at once.

[0336] The amounts of the SiH group-containing silicone and α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent weight or number average molecular weight of the SiH group-containing silicone.

[0337] Examples of catalysts used in the hydrosilylation reaction include platinum and palladium compounds, with platinum compounds being preferred, such as platinum(IV) chloride.

[0338] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted appropriately. The reaction temperature is, for example, 10 to 200°C, preferably 50 to 150°C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150°C. The hydrosilylation reaction is preferably carried out in an inert gas atmosphere. Examples of the inert gas include nitrogen and argon. The reaction proceeds even in the absence of a solvent, but a solvent may also be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0339] (Reactive Silicone) The silicone may contain a reactive silicone. Examples of reactive silicones include polysiloxanes having reactive groups on the side chain, one end, both ends, or the side chain and both ends. From the viewpoint of achieving excellent slip resistance and excellent water repellency at the same time, polysiloxanes having reactive groups on the side chain and / or both ends may also be used. The reactive silicone is not particularly limited as long as it has a reactive group in the molecule, and examples include amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, and hydrogen-modified silicone. The reactive silicone may be one in which one or more substituents in the above formula (S1) or formula (S2) have been replaced with a reactive group.

[0340] Examples of amino-modified silicones include those having a structure in which an amino group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. The alkylene group preferably has 2 or more carbon atoms. The divalent aromatic group preferably has 6 or more carbon atoms. The amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group. Examples of organic groups bonded to an amino group include the following: 2-aminoethyl group, N-methyl-2-aminoethyl group, N,N-dimethyl-2-aminoethyl group, N-ethyl-2-aminoethyl group, N,N-diethyl-2-aminoethyl group, N,N-methylethyl-2-aminoethyl group, 3-aminopropyl group, N-methyl-3-aminopropyl group, N,N-dimethyl-3-aminopropyl group, N-ethyl-3-aminopropyl group, N,N-diethyl-3-aminopropyl group, and N,N-methylethyl-3-aminopropyl group. These functional groups may be located on the side chains of the polysiloxane or at the terminals.

[0341] Epoxy-modified silicones include those having a structure in which an epoxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Typically, the bond between the organic group and the epoxy group is in the form of a glycidyl ether. Examples of such functional groups include a 3-glycidoxypropyl group and a 2-glycidoxyethyl group. These functional groups may be present on the side chain of the polysiloxane or at the terminal.

[0342] Examples of carboxy-modified silicones include those having a structure in which a carboxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. The alkylene group preferably has two or more carbon atoms. The divalent aromatic group preferably has six or more carbon atoms. Examples of such functional groups include a 3-carboxypropyl group and a 2-carboxyethyl group. These functional groups may be present on the side chain of the polysiloxane or at the terminal.

[0343] (Silicone Resin) The silicone may include a silicone resin. ３ SiO １／２ Units (M units), RSiO ３／２ Units (T units) and SiO ４／２ The silicone resin (3) is a silicone resin consisting of at least one selected from the group consisting of M units and Q units, where R is a linear or branched monovalent alkyl group having 1 to 18 carbon atoms, and excludes silicone resins consisting of only M units and only Q units). ２ SiO ２／２ It is preferable that the unit (D unit) is not contained from the viewpoint of exerting the effects of the present invention.

[0344] The silicone resin is preferably in a sol state. Examples of R include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, decyl, cetyl, and stearyl groups, but from the standpoint of stability when the silicone resin (3) is in a sol state, ease of raw material availability, and cost, R is preferably a methyl group, and it is particularly preferred that 90% or more of all R are methyl groups. Note that different types of groups may be used in combination as R.

[0345] Silicone resin with R ２ SiO ２／２ If the silicone resin contains D units, the low slip properties of the water repellent composition may be impaired. Also, if the silicone resin contains only Q units, the water repellent properties of the water repellent composition may be impaired.

[0346] Examples of the silicone resin structure include (i) silicone resins consisting of M units and Q units, (ii) M units, T units and Q units, (iii) M units and T units, (iv) T units and Q units, and (v) silicone resins consisting only of T units. (i) A silicone resin consisting of M units and Q units and (v) a silicone resin consisting only of T units are preferred. (i) The molar ratio of M units to Q units (M / Q) in a silicone resin consisting of M units and Q units is preferably M / Q = 0.6 to 1.3, more preferably M / Q = 0.8 to 1.1. Two or more of these silicone resins may be used in combination.

[0347] The silicone resin (3) may also contain a structural unit containing a hydroxyl group bonded to a silicon atom. Specifically, the structural unit may be (HO)RSiO ２／２ Units and (HO) ２ RSiO １／２ Units: (HO)SiO ３／２ Units, (HO) ２ SiO ２／２ Units, (HO) ３ SiO １／２ A part of the hydroxyl groups may be an alkoxy group represented by an RO group.

[0348] As described in Japanese Patent No. 3,852,921, a sol containing a silicone resin can be obtained by a production method in which an organodisiloxane, a tetraalkoxysilane, and their partial hydrolysis condensates are uniformly dispersed and polymerized in water containing a surfactant, or by a production method in which the following silane compound is hydrolyzed in water.

[0349] The production method of hydrolyzing a silane compound in water will now be described in detail. Any silane compound can be used as a raw material for the production, as long as the type of hydrolyzable group is chloro or alkoxy, the compound contains one, three, or four hydrolyzable groups, and the compound has an alkyl group that satisfies the above conditions.Specifically, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrichlorosilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrichlorosilane, Trichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrichlorosilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, 2-ethylhexyltrichlorosilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, decyltriethoxysilane, cetyltrichlorosilane, cetyltrimethoxysilane, cetyltriethoxy Silane, stearyl trichlorosilane, stearyl trimethoxysilane, stearyl triethoxysilane, trimethyl chlorosilane, trimethyl methoxysilane, trimethyl ethoxysilane, trimethyl isopropoxysilane, dimethyl ethyl chlorosilane, dimethyl ethyl methoxysilane, dimethyl ethyl ethoxysilane, dimethyl propyl chlorosilane, dimethyl propyl methoxysilane, dimethyl propyl ethoxysilane, dimethyl isopropyl chlorosilane, dimethyl isopropyl methoxysilane, dimethyl isopropyl ethoxysilane, di Usable silane compounds include, but are not limited to, methylhexyl chlorosilane, dimethylhexyl methoxysilane, dimethylhexyl ethoxysilane, dimethyldecyl chlorosilane, dimethyldecyl methoxysilane, dimethyldecyl ethoxysilane, dimethyl cetyl chlorosilane, dimethyl cetyl methoxysilane, dimethyl cetyl ethoxysilane, dimethylstearyl chlorosilane, dimethylstearyl methoxysilane, dimethylstearyl ethoxysilane, and partial hydrolysates thereof.From the viewpoints of operability, ease of distilling off by-products, and ease of obtaining raw materials, it is more preferable to use methoxysilane or ethoxysilane. One or a mixture of two or more of these silane compounds may be used.

[0350] Conventional methods can be used to hydrolyze silane compounds in water. These methods include adding the silane compound dropwise to water while the hydrolysis reaction is carried out, or mixing water and the silane compound together and then carrying out the hydrolysis reaction. A hydrolysis catalyst may be used when carrying out the hydrolysis reaction. Conventional catalysts can be used as the hydrolysis catalyst, and acidic or alkaline catalysts are preferred. Acidic catalysts include hydrogen halides, carboxylic acids, sulfonic acids, acidic or weakly acidic inorganic salts, and solid acids such as ion exchange resins. Alkaline catalysts include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate; alkali metal silanolates such as sodium silanolate and potassium silanolate; amines such as triethylamine, diethylamine, and aniline; and aqueous ammonia. The amount of catalyst added is preferably adjusted so that the pH of the aqueous solution is between 2 and 7 or between 7 and 12. After the reaction is complete, a neutralizing agent may be added to neutralize the acidic or alkaline catalyst, if necessary.

[0351] A surfactant may be added to the aqueous solution to disperse the silane compound and the hydrolysis reaction product in water. The surfactant is not particularly limited, but examples include anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, and alkyl phosphates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene oxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and polyoxyethylene fatty acid esters; cationic surfactants such as quaternary ammonium salts and alkylamine acetates; and amphoteric surfactants such as alkyl betaines and alkyl imidazolines. These surfactants can be used alone or in combination of two or more. Surfactants that exhibit acidic or alkaline properties can also be used as hydrolysis catalysts. The amount of surfactant added is not particularly limited, but preferably 1 to 50 parts by weight per 100 parts by weight of the silane compound. Adding less than 1 part by weight of the surfactant will not fully achieve its intended effect, while adding more than 50 parts by weight may impair the water repellency of the water repellent agent.

[0352] A hydrolysis catalyst and surfactant may be added to a mixture of water and silane compound, if necessary, and the hydrolysis reaction may be carried out at 0 to 90°C for 10 minutes to 24 hours. A neutralization reaction may then be carried out as necessary to obtain a silicone resin. Furthermore, by-products such as alcohols and neutralized salts produced by the hydrolysis reaction may be removed by vacuum distillation or filtration. Various additives may be added to this silicone resin. For example, preservatives, thickeners, etc. may be added depending on the purpose.

[0353] [Amount of Compound (C)] The amount of compound (C) in the water repellent composition may be 0.01% by weight or more, 0.03% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more, and may be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less.

[0354] The amount of polymer (A) in the water repellent composition may be 5% by weight or more, 7% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 30% by weight or more, 40% by weight or more, or 50% by weight or more, relative to the total amount of the amount of polymer (A) and the amount of compound (C), and may be 95% by weight or less, 90% by weight or less, 85% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 55% by weight or less, or 50% by weight or less. In one embodiment, the amount of polymer (A) in the water repellent composition is 5% by weight to 95% by weight relative to the total amount of the amount of polymer (A) and the total amount of compound (C).

[0355] The amount of compound (C) may be 0.01 parts by weight or more, 0.03 parts by weight or more, 0.5 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, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, or 60 parts by weight or more, relative to 100 parts by weight of the total amount of polymer (A), dispersant (B), and compound (C). It may also be 95 parts by weight or less, 90 parts by weight or less, 87 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less, 65 parts by weight or less, 60 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, 5 parts by weight or less, or 3 parts by weight or less. In one embodiment, the amount of compound (C) may be 0 parts by weight. In other words, the water repellent composition of the present disclosure may not contain compound (C). In one embodiment, the amount of the compound (C) is preferably 0 to 80 parts by weight relative to 100 parts by weight of the total amount of the polymer (A), the dispersant (B), and the compound (C).

[0356] The water repellent composition of the present disclosure may further comprise a liquid medium, an organic acid, an inorganic acid, and / or a curing agent.

[0357] [Liquid Medium] The water repellent composition of 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 composition may be a dispersion or a solution. The water repellent composition of the present disclosure is preferably an aqueous dispersion or an aqueous dispersion.

[0358] 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.

[0359] The water repellent composition of the present disclosure may be an organic solvent solution or an organic solvent dispersion. An organic solvent solution refers to a liquid in which a solute is dissolved in a solvent to form a uniform phase. An organic solvent dispersion refers to a liquid in which a solute is suspended or floated in the solvent in the form of particles, and which can be separated into a solute (dispersoid) and a solvent (dispersion medium) by centrifugation or the like.

[0360] [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 polymer (A).

[0361] 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 polymer (A).

[0362] 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, per part by weight of the polymer (A).

[0363] [Organic Acid] The water repellent composition 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.

[0364] [Amount of Organic Acid] The amount of the 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 polymer (A), 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 the organic acid may be adjusted so that the pH of the water repellent composition is 3 to 10, for example, 5 to 9, particularly 6 to 8. The water repellent composition may be acidic (pH 7 or less, for example, 6 or less).

[0365] [Inorganic Acid] The water repellent composition of the present disclosure may contain an inorganic acid. Known inorganic acids can be used. Examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In the present disclosure, one type of inorganic acid may be used, or two or more types may be used in combination. Addition of an inorganic acid can improve the stability of the aqueous dispersion.

[0366] [Amount of Inorganic Acid] The amount of inorganic 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 polymer (A), 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 inorganic acid may be adjusted so that the pH of the water repellent composition is 3 to 10, for example, 5 to 9, particularly 6 to 8. The water repellent composition may be acidic (pH 7 or less, for example, 6 or less).

[0367] [Hardening Agent] The water repellent composition of the present disclosure may contain a hardening agent (an active hydrogen-reactive compound or an active hydrogen-containing compound). When the water repellent composition is for paper (e.g., an oil-proofing agent for paper), it does not need to contain a hardening agent.

[0368] The curing agent (crosslinking agent) in the water repellent composition can satisfactorily cure the water repellent composition. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with active hydrogen or an active hydrogen-reactive group. 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, melamine compounds, and urea-based compounds.

[0369] 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 the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of an isocyanate compound is masked with a blocking agent to inhibit reaction.

[0370] 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.

[0371] 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), 1,3,5-triisocyanatocyclohexane, 4,4'methylenebis(cyclohexyl isocyanate), and 1,3-bis(isocyanatomethyl)cyclohexane. These may be used alone or in combination of two or more.

[0372] 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.

[0373] 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.

[0374] 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.

[0375] 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 composition.

[0376] 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, oxime compounds, and pyrazole compounds. The polyisocyanate compounds can be used alone or in combination of two or more.

[0377] 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.

[0378] 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 resin and methyl etherified melamine resin. Specific examples of urea compounds include dimethylol dihydroxyethylene urea (DMDHEU) and dimethyl dihydroxyethylene urea.

[0379] [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 polymer (A), 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.

[0380] The water repellent composition of the present disclosure may further comprise other ingredients.

[0381] [Other Components] The water repellent composition may contain other components in addition to the above-mentioned components. Examples of other components include water and / or oil repellents, antislip agents, antistatic agents, preservatives, antibacterial agents, deodorizers, penetrants, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components include texture adjusters, softeners, antibacterial agents, flame retardants, wrinkle inhibitors, crosslinking agents, film-forming aids, compatibilizers, UV absorbers, antioxidants, pH adjusters, insect repellents, antifoaming agents, shrinkage inhibitors, anti-wrinkle agents, shape retention agents, drape retention agents, ironing improvers, polymer dispersants, scum dispersants, fluorescent brighteners, dye fixatives, and foam inhibitors. These may be used alone or in combination of two or more.

[0382] (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. Ionic 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.

[0383] (Preservatives) Preservatives can be used primarily to enhance preservative and bactericidal properties and maintain preservative 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. The content of the preservative is preferably 0.0001 to 1 wt % relative to the total weight of the water repellent composition. When the content of the preservative is equal to or greater than the lower limit of the above range, the effect of adding the preservative can be sufficiently obtained, and when it is equal to or less than the upper limit, the storage stability of the water repellent composition is good.

[0384] (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.

[0385] (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).

[0386] (Anti-slip Agent) A component that has the effect of suppressing slippage of fibers and sewn parts during sewing or wearing. Examples of anti-slip agents include polysiloxane compounds, colloidal silicas, silicone resin derivatives, colloidal organic silicones, and amino-modified silicones.

[0387] (Softener) Softener is a component that has the effect of imparting a soft and smooth texture to fabrics. Examples of softener components include cationic surfactants such as quaternary ammonium salts and amine salts, anionic surfactants such as soap, sulfated oil, higher alcohol sulfate ester salts and sulfonate salts, nonionic surfactants such as polyhydric alcohols and polyethylene glycols, amphoteric surfactants such as betaines and amino acids, and siloxane resins.

[0388] [Amount of Other Components] The amount of each or the total amount of the other components 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 polymer (A), 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.

[0389] <Method for producing water repellent composition> The method for producing a water repellent composition may include a step of reacting (polymerizing) a silicon-containing monomer in a medium (e.g., a liquid medium) containing the silicon-containing monomer to obtain a polymer (A). The dispersant (B) may be contained in the medium, or may be combined with the polymer (A) after polymerization. The water repellent composition of the present disclosure can be obtained by such a method.

[0390] Examples of the polymerization method include suspension polymerization and emulsion polymerization, and emulsion polymerization is used from the viewpoint of obtaining an emulsion of the polymer (A). The method for obtaining the polymer (A) is the same as the polymerization method for the polymer (A) described above.

[0391] When the polymer (A) is obtained by emulsion polymerization, an emulsion containing the polymer (A) and the dispersant (B) can be obtained. The emulsion containing the polymer (A) and the dispersant (B) may be used as a water repellent composition as is. The emulsion containing the polymer (A) and the dispersant (B) may also be diluted with a liquid medium such as water and used as a water repellent composition.

[0392] When the polymer (A) is in a dry form (for example, powder), the water repellent composition of the present disclosure can be obtained by dispersing the dry form of the polymer (A) together with the dispersant (B) in a liquid medium.

[0393] In one embodiment, the method for producing a water repellent composition may further include a step of obtaining at least one compound (C) selected from the group consisting of a vinyl polymer, an isocyanate derivative, a wax, and a silicone, and a step of combining the polymer (A), the dispersant (B), and the compound (C).

[0394] The vinyl polymer, isocyanate derivative, wax, and silicone may be commercially available products, or may be obtained by the polymerization method described above for the compound (C).

[0395] The compound (C) in the step of obtaining the compound (C) may be in a dry form (e.g., powder) or in a state of dispersion in a liquid medium. When the compound (C) is in a state of dispersion in a dispersion, the dispersion may contain a dispersant (B).

[0396] The step of combining the polymer (A), dispersant (B), and compound (C) is not particularly limited, and may involve combining a dispersion containing the polymer (A) and dispersant (B-1) with a dispersion containing the compound (C) and dispersant (B-2). Here, the dispersants (B-1) and (B-2) are each independently dispersants selected from the dispersants (B).

[0397] A dispersion containing the polymer (A) and the dispersant (B-1) can be obtained by obtaining the polymer (A) by emulsion polymerization using the dispersant (B-1) or by dispersing the polymer (A) in a liquid medium using the dispersant (B-1). A dispersion containing the compound (C) and the dispersant (B-2) can be obtained by obtaining a vinyl polymer, silicone, or the like by emulsion polymerization using the dispersant (B-2), or by dispersing a vinyl polymer, an isocyanate derivative, a wax, or silicone in a liquid medium using the dispersant (B-2).

[0398] <Applications of Water Repellent Composition> Examples of applications of the water repellent composition according to the present disclosure include an external treatment agent (surface treatment agent) or an internal treatment agent, a water repellent composition (a water repellent, an oil repellent, or a water and oil repellent, particularly a water repellent), an antifouling agent, a soil release agent, a stripping agent, a release agent (an external release agent or an internal release agent), and the like.

[0399] <Method for Producing Treated Product> The method for producing a treated product in the present disclosure includes treating a substrate with a water repellent composition.

[0400] [Treated Products] Substrates that can be treated with the water repellent composition of the present disclosure include fibrous substrates, stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Various examples of fibrous substrates can be mentioned. Examples include natural fibers of animal and plant origin such as cotton, linen, 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; and mixtures thereof. Woven and knitted fabrics are described in detail below as an example of a substrate that can be treated with the water repellent composition.

[0401] (Woven and knitted fabrics) - Manufacturing method of woven and knitted fabrics Woven and knitted fabrics can be obtained by weaving and knitting long and short fiber yarns made of the above-mentioned fibers to obtain a greige fabric, which is then post-processed and subjected to a water-repellent treatment. The weaving and knitting can be performed using known looms and knitting machines, and known equipment can also be used for the preparation process prior to the weaving and knitting.

[0402] The woven or knitted fabric can be post-processed using known scouring and dyeing methods and equipment suited to the fiber material of the woven or knitted fabric.

[0403] After the post-processing, the woven or knitted fabric may be subjected to a water-repellent treatment. In the water-repellent treatment, first, an aqueous solution containing a water repellent (which may be the water-repellent composition of the present disclosure) is prepared. Next, the aqueous solution is applied to the woven or knitted fabric after the post-processing using a padding method, a spray method, a kiss roll coater method, a slit coater method, or the like, and then dried and subjected to a dry heat treatment. The aqueous solution may also contain a crosslinking agent, a softener, an antistatic agent, or the like, as necessary. After the water-repellent treatment, the woven or knitted fabric may be calendered.

[0404] The woven and knitted fabrics are suitable for use in clothing applications where water repellency is required, particularly in sportswear applications for outdoor activities, skiing, snowboarding, golf, etc., and uniform applications.

[0405] The woven / knitted fabric of the present disclosure may be provided as a laminated fabric having a moisture-permeable waterproof layer on one side thereof. The moisture-permeable waterproof layer may be laminated directly onto the woven / knitted fabric, or may be laminated onto the woven / knitted fabric via an adhesive layer. When the laminated fabric of the present disclosure is used for clothing or the like, the woven / knitted fabric side is arranged to repel rainwater and the like.

[0406] - Moisture-permeable waterproof layer The moisture-permeable waterproof layer is a layer that covers one side of a woven or knitted fabric, and is a layer formed of a waterproof and moisture-permeable resin or structural film.

[0407] The moisture-permeable waterproof layer may be formed by applying a resin (the resin that constitutes the moisture-permeable waterproof layer) directly to the woven or knitted fabric, or may be laminated to one side of the woven or knitted fabric via an adhesive layer described below.

[0408] The resin that constitutes the moisture-permeable waterproof layer is not particularly limited, but non-porous and porous resins are used. For non-porous ones, polyurethane resins and polyester elastomer resins that contain hydrophilic components are used to provide moisture permeability. For porous ones, polyurethane resins that form wet-process porous membranes and polyurethane resins that are made porous by electrospinning are used, as well as porous PTFE membranes and porous membranes made of PE or PP.

[0409] As the polyurethane resin, a conventionally known resin obtained by reacting a polyisocyanate component with a polyol component can be used.

[0410] A moisture-permeable waterproof membrane having a microporous structure can be obtained by wet coagulation of a DMF solution of a polyurethane resin containing an inorganic fine powder. Examples of inorganic fine powder include fine powders made of silicon dioxide, aluminum dioxide, or titanium dioxide. The average primary particle size of the inorganic fine powder is preferably about 7 to 40 nm. The content of the inorganic fine powder is preferably 3 to 50 wt %, and more preferably 5 to 50 wt %, of the total weight of the moisture-permeable waterproof layer.

[0411] The thickness of the moisture-permeable waterproof layer is preferably 5 μm or more, and more preferably 10 to 30 μm. A thickness within this range provides an excellent balance between waterproofness and moisture permeability, and is also advantageous in terms of texture.

[0412] The adhesive layer laminated fabric preferably includes an adhesive layer. That is, the woven or knitted fabric and the moisture-permeable waterproof layer are preferably laminated via an adhesive layer. In terms of moisture permeability, the adhesive layer is preferably a discontinuous layer such as a dot or grid pattern.

[0413] The type of adhesive that constitutes the adhesive layer is not particularly limited, but it is preferable that it has excellent adhesion to the moisture-permeable waterproof layer. For example, if a resin containing polyurethane resin as the main component is selected as the resin that constitutes the moisture-permeable waterproof layer, it is preferable to use an adhesive layer made of a polyurethane-based adhesive. The polyurethane-based adhesive may be any of ether-based, ester-based, polycarbonate-based, etc.

[0414] The adhesive layer may be formed over the entire surface of one side of the woven or knitted fabric, or may be formed in a pattern from the viewpoint of moisture permeability, texture, etc. The pattern shape is not particularly limited, but examples include dots, lines, a grid, a checkerboard pattern, a tortoiseshell pattern, etc., and it is preferable that any of these patterns be uniformly arranged over the entire surface.

[0415] The thickness of the adhesive layer is preferably about 10 to 100 μm, and more preferably 20 to 80 μm.

[0416] In the laminated fabric of the present disclosure, a lining fiber fabric may be laminated on the moisture-permeable waterproof layer (on the side of the moisture-permeable waterproof layer opposite to the side on which the woven or knitted fabric of the present disclosure is laminated). The lining fiber fabric can protect the moisture-permeable waterproof layer and can provide even better waterproofness (water pressure resistance) and strength.

[0417] Examples of the fiber fabric for the lining include various woven fabrics, knitted fabrics, etc. Among them, knitted fabrics are preferred because, compared with woven fabrics, the constituent yarns are more likely to protrude from the surface, resulting in an uneven surface, and the knitted fabric exhibits a stronger anchoring effect, making it less likely to peel off from the moisture-permeable waterproof layer.

[0418] Furthermore, tricot knitted fabrics are also preferred in that they can be produced as long grey fabrics during knitting, have few seams, and can be evenly layered on the moisture-permeable waterproof layer.

[0419] The material of the fibers constituting the lining fiber fabric is not particularly limited and can be selected as appropriate, but nylon fiber is preferred. This is because acid dyes are generally used in nylon fibers, which makes it less likely for the disperse dye to migrate and sublimate into the moisture-permeable waterproof layer, a problem that occurs with polyester fibers, etc., which use disperse dyes. The form (long fiber, short fiber, or spun yarn) or fineness of the fibers constituting the lining fiber fabric are not particularly limited and can be selected as appropriate as long as the effects of the present disclosure are not impaired.

[0420] The laminated fabric has excellent waterproof properties. A suitable example of the waterproof properties of the laminated fabric of the present disclosure is a water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method) of 10,000 mm or more, preferably 15,000 mm or more, more preferably 16,000 mm or more, and particularly preferably 20,000 mm or more.

[0421] The laminated fabric has excellent moisture permeability. A preferred example of the moisture permeability of the laminated fabric of the present disclosure is a moisture permeability of, for example, 10,000 g / m2, as measured in accordance with JIS L 1099:2021 B-1 method (potassium acetate method). 2 24 hours or more, preferably 15,000 g / m 2 24 hours or more, more preferably 20,000 g / m 2 The upper limit of the moisture permeability is not particularly limited, but is, for example, 40,000 g / m 2 24h or 35,000g / m 2 24h mm. In addition, the moisture permeability measured in accordance with JIS L 1099:2021 A-1 method (calcium chloride method) is, for example, 4000 g / m 2 24 hours or more, preferably 8000 g / m 2 24 hours or more, more preferably 10,000 g / m 224 hours or more. The upper limit of the moisture permeability is 13,000 to 15,000 g / m2, which is the limit of the measurement method. 2 ・It will take about 24 hours.

[0422] In the laminated fabric of the present disclosure, the peel strength between the woven or knitted fabric and the breathable waterproof layer, as measured in accordance with the method of JIS K 6404-2, is preferably 2.55 N / 2.54 cm or more for clothing applications, and may be preferably 5 N / 2.54 cm or more for use in applications.

[0423] - Manufacturing method of laminated fabric There are no particular limitations on the manufacturing method of the laminated fabric, and examples include the first manufacturing method and the second manufacturing method shown below. First manufacturing method: Includes a step of forming the moisture-permeable waterproof layer by applying a resin that constitutes the moisture-permeable waterproof layer to the surface of a woven or knitted fabric. Second manufacturing method: Includes a step of forming an adhesive layer on the woven or knitted fabric or the moisture-permeable waterproof layer, and a step of bonding the woven or knitted fabric and the moisture-permeable waterproof layer via the adhesive layer.

[0424] In the first manufacturing method, the resin that constitutes the moisture-permeable waterproof layer can be applied to the surface of the woven or knitted fabric by, for example, a coating method. A knife coater or a comma coater can be used in the coating method. From the viewpoint of providing excellent moisture permeability, it is preferable to obtain the moisture-permeable waterproof layer by a wet method.

[0425] In the second manufacturing method, examples of techniques for forming an adhesive layer on a woven or knitted fabric or a moisture-permeable waterproof layer include lamination. In the lamination method, a resin solution or a hot-melt method can be used to form the adhesive layer. First, a moisture-permeable waterproof layer-forming resin composition (e.g., a resin composition containing a resin and an organic solvent) is applied to the surface of a release material (such as release paper, release cloth, or release film) with a clearance, and a moisture-permeable waterproof layer is formed while adjusting the thickness. The film is then dried and heat-treated to obtain a film. The release material can be removed as appropriate after lamination or aging. Furthermore, when laminating using a hot-melt method, the release material can be peeled off and the film can be laminated alone. Furthermore, the moisture-permeable waterproof membrane can be formed by laminating a membrane produced by a solventless extrusion method such as the T-die method or inflation method, a porous membrane produced by electrospinning, or a porous membrane made of PTFE, PE, PP, or the like.

[0426] An adhesive layer is then formed on the woven or knitted fabric or the moisture-permeable waterproof layer. For example, in the case of a method using a resin solution, a two-component curing polyurethane resin solution adjusted to a viscosity in the range of 500 to 5,000 mPa·s may be applied to the entire surface or in a pattern. The resulting solution is then dried to form an adhesive layer, and the woven or knitted fabric and the moisture-permeable waterproof layer are bonded together via the adhesive layer, and the two are then pressure-bonded or thermocompression-bonded, thereby completing the second manufacturing method.

[0427] On the other hand, in the case of hot melt, it is preferable to use a moisture-curing resin that reacts with moisture in the air, and in practical use, it is more preferable to use one that melts in a temperature range of about 80 to 150°C. In this case, the hot melt resin is first melted while taking into consideration the melting point of the resin and its viscosity when melted. The second manufacturing method can then be carried out by applying the molten resin to the woven or knitted fabric or the moisture-permeable waterproof layer to form an adhesive layer, and bonding the woven or knitted fabric and the moisture-permeable waterproof layer together under pressure. Alternatively, if texture is important, the resin can be applied in a pattern to the moisture-permeable waterproof membrane and then bonded to the woven or knitted fabric.

[0428] Thereafter, a lining fiber fabric can be laminated on the moisture-permeable waterproof layer using any known appropriate method.

[0429] - Uses of laminated fabrics: Laminated fabrics have excellent water repellency and breathable waterproof properties, and the breathable waterproof layer does not peel off even in harsh environments, making them suitable for use in fields such as uniforms, sportswear, and outdoor products used outdoors.

[0430] [Treatment Method] The water repellent composition of the present disclosure can be applied to a substrate (particularly a fiber substrate) as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The water repellent composition of the present disclosure may be dispersed and diluted in an organic solvent or water, if necessary, and applied to the surface of the substrate by a known method such as dip coating, spray coating, foam coating, or the like, followed by drying. After drying, a fiber product is obtained to which the solid components of the water repellent composition are attached. If necessary, the composition may be applied together with an appropriate crosslinking agent and cured. Furthermore, the water repellent composition 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 in the "other components" section of the water repellent composition. The concentration of the hydrocarbon-based water repellent resin 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.

[0431] [Textile Products] Various examples of the fiber substrate as the base material include cloth products and paper products.

[0432] Examples of textile products include natural fibers of animal or plant origin such as cotton, linen, wool, silk, etc., synthetic fibers such as polyamide, polyester (particularly polyethylene terephthalate is preferred), polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc., semi-synthetic fibers such as rayon, acetate, etc., inorganic fibers such as glass fiber, carbon fiber, asbestos fiber, etc., or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics, nonwoven fabrics, clothing fabrics, 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 textiles.

[0433] Examples of 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 paper, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating mediums, neutral white roll paper, neutral liners, rust-proof liners 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.

[0434] The water repellent composition can be applied to a textile substrate (e.g., fabric) by any of the known methods for treating the textile substrate with a liquid. The textile substrate may be immersed in the water repellent composition, or the solution may be applied or sprayed onto the textile substrate. The treated textile substrate is preferably dried and cured by heating to develop water and oil 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.

[0435] Alternatively, the polymer may be applied to the fibrous substrate by a cleaning process, such as in a laundry application or a dry cleaning process.

[0436] The treated fiber substrate may be a fabric, including woven fabrics, knitted fabrics, and nonwoven fabrics, clothing fabrics, carpets, etc., but may also be a fiber or yarn or intermediate fiber product (e.g., sliver or roving, etc.). The water repellent composition of the present disclosure is particularly effective in making textiles (e.g., synthetic fibers) water repellent.

[0437] The fibers constituting the fibrous substrate may be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, or inorganic fibers. The fibers may be used alone or in combination of two or more types.

[0438] Examples of natural fibers include cellulosic fibers such as cotton, flax, and pulp, chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as ground wood pulp (GP), pressure-raised ground wood pulp (PGW), and thermomechanical pulp (TMP), chemical pulps such as high-yield unbleached softwood kraft pulp (HNKP; N wood), bleached softwood kraft pulp (NBKP; N wood, NB wood), unbleached hardwood kraft pulp (LUKP; L wood), and bleached hardwood kraft pulp (LBKP, L wood), recycled paper pulps such as deinking pulp (DIP) and waste pulp (WP), and semi-chemical pulp (CP).

[0439] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymer polyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupra, polynosic rayon, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0440] Alternatively, the fibrous substrate may be leather. The manufacturing polymer may be applied to the leather from an aqueous solution or emulsion at various stages of leather processing, for example, during the wet processing of the leather or during the finishing of the leather, to render the leather hydrophobic and oleophobic. Alternatively, the fibrous substrate may be paper. The manufacturing polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example, during the drying of the paper.

[0441] The term "treatment" means applying the water repellent composition to a substrate by immersion, spraying, coating, or the like. The treatment allows the polymer (A), which is the active ingredient of the water repellent composition, to penetrate into the substrate and / or adhere to the surface of the substrate. In other words, the treatment results in a substrate (e.g., a textile product) having the polymer (A) in the water repellent composition of the present disclosure adhered thereto.

[0442] [Pretreatment of Fiber Substrate] The fiber substrate may be pretreated before being treated with the water repellent composition of the present disclosure. Pretreatment of the fiber substrate can impart excellent fastness to the fiber substrate after treatment with the water repellent composition.

[0443] Examples of pretreatments of fiber substrates 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.

[0444] The method for pretreating the fibrous substrate is not limited, and the fibrous substrate 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 surface of the fibrous substrate 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 fibrous substrate, a method for pretreating a fibrous substrate with a hydrocarbon-based water repellent will be described in detail.

[0445] The pretreatment method for the fiber substrate is to add -SO ３ M １ (In the formula, M １represents 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 a "specific functional group").

[0446] 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 X ２ 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.

[0447] 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.

[0448] 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.

[0449] The raw 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 of fibers (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, paper, etc.

[0450] 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.

[0451] 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:

[0452] [In the formula, X ２ 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.

[0453] [In the formula, M ４ represents a monovalent cation.

[0454] The above M ３ Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0455] The above M ４ Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0456] 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.

[0457] Above - COOM ２ Examples of compounds having the formula include polycarboxylic acid polymers.

[0458] 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.

[0459] 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.

[0460] 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.

[0461] 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.

[0462] 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.

[0463] 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.

[0464] 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.

[0465] 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.

[0466] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0467] 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.

[0468] 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.

[0469] 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.

[0470] 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.

[0471] The treatment temperature in the immersion treatment can be 60 to 130° C. The treatment time can be 5 to 60 minutes.

[0472] 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.

[0473] The pH of the pretreatment liquid is preferably adjusted to 3 to 5. The pH can be adjusted using a pH adjuster such as acetic acid or malic acid.

[0474] 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.

[0475] 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 a hydrocarbon-based water repellent.

[0476] (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).

[0477] 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.).

[0478] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0479] <Test Method> The test procedure is as follows.

[0480] The following instruments were used for analyzing the molecular weight: Measurement by gel permeation chromatography (GPC) (hereinafter referred to as "GPC measurement") Apparatus: HLC-8420GPC EcoSEC Elite-WS (manufactured by Tosoh Corporation) Column: TSKgel SuperMultiporeHZ-M (manufactured by Tosoh Corporation) Column temperature: 40°C Solvent: tetrahydrofuran Flow rate: 0.35 mL / min Detector: differential refractive index detector

[0481] [Water Repellency Test] The water repellency of the test cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). The water repellency was evaluated according to the following criteria. The higher the score, the better the water repellency, and intermediate scores (95, 85, 75) were assigned depending on the condition.

[0482] 100 No wetting or water droplets were observed on the surface. 90 No wetting on the surface, but small water droplets were observed. 80 Small individual water droplets were observed on the surface. 70 Wetting was observed on half of the surface, with small individual wettings penetrating the fabric. 50 Wetting was observed on the entire surface. 0 Wetting was observed on both the front and back surfaces.

[0483] [Light Oil Repellency Test] 0.05 mL of the test liquid was dropped onto a test cloth from a height of 0.6 cm. The above procedure was repeated, with five drops dropped onto the cloth at 4.0 cm intervals. Light oil repellency was evaluated by observing the penetration and shape of the oil droplets after 30±2 seconds. The test liquid was prepared by mixing PEG-600 and oleic acid in a mass ratio of 9:1. The surface tension of this test liquid was measured using an automatic surface tensiometer DY-300 (manufactured by Kyowa Interface Science Co., Ltd.) and found to be 35.7 mN / m. Light oil repellency was evaluated according to the following criteria: A indicates the best light oil repellency, and D indicates extremely poor light oil repellency. The results of three or more of the five dropped drops were used as the evaluation value. Depending on the condition, an intermediate value (A-, B-, C+) was assigned.

[0484] A [Wetting / Penetration] Transparent (not wet) [Shape of oil droplet] Rounded B [Wetting / Penetration] Slightly darkened edges and bottom [Shape of oil droplet] Rounded C [Wetting / Penetration] Partial penetration observed [Shape of oil droplet] Contact angle 35° or less D [Wetting / Penetration] Completely penetrated [Shape of oil droplet] Flat

[0485] [Slip resistance test] The test was conducted according to ISO 13936-2 except that the load was set to 160 N, and seam slippage (mm) was measured. A smaller seam slippage value indicates better slip resistance, and a value equivalent to that of an untreated fabric, i.e., 2.0 mm or less, is most preferable.

[0486] [Preparation of Raw Materials] (Production Examples of Aqueous Dispersions Containing Silicon-Containing Polymers) Production Example 1 A 500 mL plastic container was charged with 2.76 g of a water-soluble glycol solvent as an organic solvent, 62.2 g of pure water as a liquid medium, 27.6 g of 3-(methacryloyloxy)propyltris(trimethylsilyloxy)silane (manufactured by JNC Corporation, product name: TM-0701T) as a silicon-containing (meth)acrylate, 0.52 g of a cationic dispersant as a dispersant, 2.14 g of a sorbitan fatty acid ester, and 1.48 g of a polyoxyethylene alkyl ether, and the mixture was heated to 70°C and stirred at 1000 rpm with a homomixer for 1 minute, followed by emulsification and dispersion with ultrasound for 15 minutes. Next, this emulsified dispersion was transferred to a 200 mL four-neck flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux condenser. After nitrogen substitution, 0.14 g of an azo group-containing water-soluble initiator was added, and the mixture was heated to 60°C and reacted for 3 hours to obtain an aqueous dispersion of a polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a non-volatile content of 30%. When the polymer in this dispersion was subjected to GPC measurement, the number average molecular weight was found to be 305,000.

[0487] Preparation Example 2: A 500 mL plastic container was charged with 2.76 g of a water-soluble glycol solvent as an organic solvent, 62.2 g of pure water as a liquid medium, 27.6 g of 3-(methacryloyloxy)propyltris(trimethylsilyloxy)silane (manufactured by JNC Corporation, product name: TM-0701T) as a silicon-containing (meth)acrylate, 0.52 g of a cationic dispersant as a dispersant, 2.14 g of sorbitan fatty acid ester, and 1.48 g of polyoxyethylene alkyl ether, heated to 60 ° C., stirred at 800 rpm with a magnetic stirrer for 1 minute, and then ultrasonically emulsified and dispersed for 5 minutes. Next, this emulsified dispersion was transferred to a 200 mL four-neck flask equipped with a nitrogen inlet tube, thermometer, stirrer, and reflux condenser. After nitrogen substitution, 0.14 g of an azo group-containing water-soluble initiator was added, heated to 60 ° C., and reacted for 3 hours to obtain an aqueous dispersion of a polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a nonvolatile content of 30%. When the polymer in this dispersion was subjected to GPC measurement, the number average molecular weight was found to be 1,400,000.

[0488] Production Example 3 A 500 mL plastic container was charged with 2.76 g of a water-soluble glycol solvent as an organic solvent, 62.2 g of pure water as a liquid medium, 27.6 g of 3-(methacryloyloxy)propyltris(trimethylsilyloxy)silane (manufactured by JNC Corporation, product name: TM-0701T) as a silicon-containing (meth)acrylate, 0.52 g of a cationic dispersant as a dispersant, 2.14 g of a sorbitan fatty acid ester, and 1.48 g of a polyoxyethylene alkyl ether, and the mixture was heated to 70°C, stirred at 1000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. Next, this emulsified dispersion was transferred to a 200 mL four-neck flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux condenser. After nitrogen substitution, 0.028 g of lauryl mercaptan was charged and stirred, and then 0.14 g of an azo group-containing water-soluble initiator was added. The temperature was raised to 60 ° C. and the reaction was carried out for 3 hours to obtain an aqueous dispersion of a polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a non-volatile content of 30%. Note that when GPC measurement was performed on the polymer in this dispersion, the number average molecular weight was found to be 114,000.

[0489] Production Example 4 A 500 mL plastic container was charged with 1.38 g of a water-soluble glycol solvent as an organic solvent, 62.2 g of pure water as a liquid medium, 26.2 g of 3-(methacryloyloxy)propyltris(trimethylsilyloxy)silane (manufactured by JNC Corporation, product name: TM-0701T) as a silicon-containing (meth)acrylate, 2.76 g of stearyl acrylate as a comonomer, 0.52 g of a cationic dispersant as a dispersant, 2.14 g of a sorbitan fatty acid ester, and 1.48 g of a polyoxyethylene alkyl ether, and the mixture was heated to 70°C, stirred at 1000 rpm with a homomixer for 1 minute, and then emulsified and dispersed with ultrasound for 15 minutes. The emulsified dispersion was transferred to a 200 mL four-neck flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux condenser. After nitrogen substitution, 0.14 g of an azo group-containing water-soluble initiator was added, and the mixture was heated to 60°C and reacted for 4 hours to obtain an aqueous dispersion of a polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a nonvolatile content of 30%. GPC measurement of the polymer in this dispersion revealed that the number average molecular weight was 370,000.

[0490] Preparation Example 1: A 500 mL plastic container was charged with 30 g of a water-soluble glycol solvent as an organic solvent, 120 g of pure water as a liquid medium, 48 g of stearyl acrylate as a long-chain aliphatic hydrocarbon group-containing (meth)acrylate, 0.46 g of a cationic dispersant as a dispersant, 2.0 g of sorbitan fatty acid ester, 6.0 g of polyoxyethylene alkyl ether, and 0.1 g of acetic acid. The mixture was heated to 60°C, stirred at 2000 rpm with a homomixer for 1 minute, and then emulsified and dispersed with ultrasound for 15 minutes. The resulting emulsion was then transferred to a 500 mL autoclave, purged with nitrogen, and charged with 0.2 g of lauryl mercaptan and 12 g of vinyl chloride as chain transfer agents. 1.0 g of an azo group-containing water-soluble initiator was then added, heated to 60°C, and reacted for 4 hours to obtain an aqueous dispersion of a polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a nonvolatile content of 30%.

[0491] Preparation Example 2 An aqueous dispersion containing an acrylic polymer, a surfactant, and a liquid medium was prepared in the same manner as in Preparation Example 1, except that the long-chain aliphatic hydrocarbon group-containing (meth)acrylate was changed to 24 g of stearyl acrylate and 24 g of stearyl group-containing amide acrylate. This dispersion was further diluted with pure water to obtain an aqueous dispersion with a nonvolatile content of 30%.

[0492] Preparation Example 3: In a 200 mL four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser, methylhydrogen silicone oil (SiH:SiCH as measured by 1H NMR) was added. ３ 12 g of 1-hexacosene (molar ratio = 50:50) and 0.02 g of platinum catalyst were charged. Next, 36 g of 1-hexacosene was charged into the dropping funnel, and while maintaining the temperature at 70°C, 1-hexacosene was added dropwise from the dropping funnel. After completion of the dropwise addition, the reaction was continued for another 3 hours at 70°C. The disappearance of the SiH peak was confirmed by infrared spectroscopy (IR), yielding 47 g of solid silicone polymer. 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 dispersant were charged into a 250 mL glass container, heated to 75°C, stirred at 2000 rpm with a homomixer for 1 minute, and then ultrasonically emulsified and dispersed for 10 minutes to obtain an aqueous dispersion of the silicone polymer. This dispersion was then diluted with pure water to prepare an aqueous dispersion with a nonvolatile content of 30%.

[0493] Preparation Example 4: A 500 mL plastic container was charged with 30 g of water-soluble glycol solvent as the organic solvent, 120 g of pure water as the liquid medium, 60 g of stearyl acrylate, and 2.0 g of cationic emulsifier, 2.0 g of sorbitan fatty acid ester, and 6.0 g of polyoxyethylene alkyl ether as dispersants. The mixture was heated to 80°C and stirred at 2000 rpm with a homomixer for 1 minute, followed by ultrasonic emulsification for 15 minutes. The emulsified dispersion was transferred to a 500 mL four-neck flask equipped with a nitrogen inlet tube, thermometer, stirrer, and reflux condenser. After nitrogen substitution, 0.2 g of lauryl mercaptan was charged and stirred. 1.0 g of azo-group-containing water-soluble initiator was added, and the mixture was heated to 60°C and allowed to react for 4 hours to obtain an aqueous dispersion of a polymer. Pure water was then added to prepare an aqueous dispersion with a nonvolatile content of 30%.

[0494] Preparation Example 5 1. Synthesis of Aliphatic Polyisocyanate 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, 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, and then 10.7 parts by mass of 1,3-butanediol was added to this 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 aliphatic polyisocyanate derivative had an isocyanate group content of 20.9% and an average number of isocyanate functional groups of 3.0.

[0495] 2. Production of Hydrocarbon-Based Polyurethane: 100.20 g of the aliphatic polyisocyanate derivative, 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% by weight or more. The nonvolatile content excluding the acid compound (acetic acid) was then adjusted with ion-exchanged water to 20%, thereby obtaining an aqueous dispersion containing polyurethane.

[0496] Preparation Example 6: 150 g of paraffin wax (melting point 75°C), 350 g of pure water, 4.5 g of polyoxyethylene alkyl ether, and 3 g of sorbitan fatty acid ester were placed in a pressure reactor, which was then sealed. The mixture was heated to 110 to 120°C with stirring, and then emulsified under high pressure for 30 minutes to prepare an aqueous dispersion of wax. Pure water was then added to prepare an aqueous dispersion of wax with a nonvolatile content of 30%.

[0497] Comparative Production Example 1 A 500 mL plastic container was charged with 2.76 g of a water-soluble glycol solvent as an organic solvent, 62.23 g of pure water as a liquid medium, 27.6 g of 3-(methacryloyloxy)propyltris(trimethylsilyloxy)silane (manufactured by JNC Corporation, product name: TM-0701T) as a silicon-containing (meth)acrylate, and 2.25 g of a cationic emulsifier, 2.14 g of a sorbitan fatty acid ester, and 1.48 g of a polyoxyethylene alkyl ether as a dispersant. The mixture was heated to 70°C, stirred at 1000 rpm with a homomixer for 1 minute, and then emulsified and dispersed with ultrasound for 15 minutes. Next, this emulsified dispersion was transferred to a 200 mL four-neck flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux condenser. After nitrogen substitution, 0.28 g of lauryl mercaptan was charged and stirred, and then 0.14 g of an azo group-containing water-soluble initiator was added. The temperature was raised to 60 ° C. and the reaction was carried out for 3 hours to obtain an aqueous dispersion of a polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a non-volatile concentration of 30%. Note that when GPC measurement was performed on the polymer in this dispersion, the number average molecular weight was found to be 21,100.

[0498] Comparative Production Example 2 A 500 mL plastic container was charged with 30 g of a water-soluble glycol solvent as an organic solvent, 120 g of pure water as a liquid medium, 16.6 g of 3-(methacryloyloxy)propyltris(trimethylsilyloxy)silane (manufactured by JNC Corporation, product name: TM-0701T) as a silicon-containing (meth)acrylate, 11.0 g of stearyl acrylate as a comonomer, 2.25 g of a cationic emulsifier as a dispersant, 2.14 g of a sorbitan fatty acid ester, and 1.48 g of a polyoxyethylene alkyl ether, and the mixture was heated to 70°C, stirred at 1000 rpm with a homomixer for 1 minute, and then emulsified and dispersed with ultrasound for 15 minutes. The emulsified dispersion was transferred to a 200 mL four-neck flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux condenser. After nitrogen substitution, 0.14 g of an azo group-containing water-soluble initiator was added, and the mixture was heated to 60°C and reacted for 4 hours to obtain an aqueous dispersion of a polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a non-volatile concentration of 30%. GPC measurement of the polymer in this dispersion revealed that the number average molecular weight was 350,000.

[0499] Example 1 An organosilicon polymer dispersion and tap water were mixed to obtain the composition shown in Table 1 (in which the values ​​indicate (wt%)), to obtain a treatment solution of a water repellent composition. Polyester cloth, nylon cloth, and polyester / polyurethane (PU) cloth were immersed in this treatment solution and then wrung out with a mangle. The treated cloths were passed through a pin tenter at 170°C for 1 minute, dried, and cured. The treated test cloths were used to test for water repellency, light oil repellency, and slip resistance. The results are shown in Table 1.

[0500] Examples 2 to 15 and Comparative Examples 1 to 7 Test cloths were prepared and tested for water repellency, light oil repellency, and slip resistance in the same manner as in Example 1, except that the compounding formulations were changed according to Table 1. The results are shown in Table 1.

[0501]

Claims

The following formula: HH ２ =C(-R ａ )-+-SiZ ３ [In the formula: R ａ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, X is X １ and X ２ is a divalent group consisting of one or more members selected from the group consisting of X １ is a group consisting of one or more selected from the group consisting of —O—, —C(═O)—, and —NR′— (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms); X ２ is a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, Each Z is independently a hydrocarbon group having 1 to 10 carbon atoms or -(O-SiZ １ ２ ) ｎ -O-SiZ ２ ３ and Z １ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ １１ ３ and Z １１ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ １１１ ３ and Z １１１ are each independently a hydrocarbon group having 1 to 10 carbon atoms, Z ２ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ ２１ ３ and Z ２１ are each independently a hydrocarbon group having 1 to 10 carbon atoms or —OSiZ ２１１ ３ and Z ２１１ are each independently a hydrocarbon group having 1 to 10 carbon atoms, Each n is independently an integer from 0 to 196. and a dispersant (B), The polymer (A) contains repeating units derived from the silicon-containing monomer in an amount of 90% by weight or more based on the weight of the polymer (A), and The water repellent composition, wherein the polymer (A) has a number average molecular weight of 60,000 or more and 4,000,000 or less. X is -X １ -X ２ - [In the formula, X １ is —C(═O)—O—, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′—C(═O)—O—, —NR′—C(═O)—NR′—, —C(═O)—, or —C(═O)—NR′— (wherein R′ in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms); X ２ is a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms. The water repellent composition according to claim 1, wherein the group is a group represented by the formula: Z １ are each independently -OSiZ １１ ３ and Z １１ are each independently an alkyl group having 1 to 3 carbon atoms, Z ２ are each independently -OSiZ ２１ ３ and Z ２１ The water repellent composition according to claim 1 or 2, wherein each of the groups independently represents an alkyl group having 1 to 3 carbon atoms. X ２ The water repellent composition according to any one of claims 1 to 3, wherein is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms. The water repellent composition according to any one of claims 1 to 4, wherein n is 0. The water repellent composition according to any one of claims 1 to 5, wherein the polymer (A) contains repeating units derived from the silicon-containing monomer in an amount of 96 wt% or more based on the weight of the polymer (A). The water repellent composition according to any one of claims 1 to 6, wherein the polymer (A) has a number average molecular weight of 2,000,000 or less. The water repellent composition according to any one of claims 1 to 7, wherein the dispersant (B) comprises a cationic dispersant. The water repellent composition according to any one of claims 1 to 8, comprising at least one compound (C) selected from the group consisting of vinyl polymers, isocyanate derivatives, waxes, and silicones.

10. The water repellent composition according to claim 9, wherein the amount of the polymer (A) in the water repellent composition is 5% by weight to 95% by weight based on the total amount of the polymer (A) and the compound (C). The water repellent composition according to claim 9, wherein the compound (C) is a polymer containing a repeating unit derived from a hydrocarbon group-containing monomer having a hydrocarbon group having 2 to 40 carbon atoms. The hydrocarbon group-containing monomer is represented by the following formula: CH ２ =C(-R ｂ )-C(=O)-R ｃ -(R ｄ ) ｋ [In the formula, R ｂ is a hydrogen atom, a monovalent organic group, or a halogen atom, R ｃ represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -S-, -C(=O)-, -S(=O) ２ - and -NR Ｃ１ - (R Ｃ１ is a divalent to tetravalent group consisting of at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms, k is 1 to 3; R ｄ are each independently a hydrocarbon group having 2 to 40 carbon atoms. The water repellent composition according to claim 11, wherein the monomer is represented by the formula: X is -X １ -X ２ - [In the formula, X １ is —C(═O)—O—, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′—C(═O)—O—, —NR′—C(═O)—NR′—, —C(═O)—, or —C(═O)—NR′— (wherein R′ in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms); X ２ is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms. n is 0, Z ２ are each independently an alkyl group having 1 to 3 carbon atoms, The following formula: CH ２ =C(-R ｂ )-C(=O)-R ｃ -(R ｄ ) ｋ [In the formula, R ｂ is a hydrogen atom, a monovalent organic group, or a halogen atom, R ｃ represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -S-, -C(=O)-, -S(=O) ２ - and -NR Ｃ１ - (R Ｃ１ is a divalent to tetravalent group consisting of at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms, k is 1 to 3; R ｄ is a hydrocarbon group having 2 to 40 carbon atoms. The polymer further comprises a compound (C) which is a polymer containing a repeating unit derived from a hydrocarbon group-containing monomer represented by the formula:

2. The water repellent composition according to claim 1, wherein the amount of the polymer (A) in the water repellent composition is 5% by weight to 95% by weight based on the total amount of the polymer (A) and the compound (C). R ａ is a hydrogen atom or a methyl group, X is -X １ -X ２ - [In the formula, X １ is —C(═O)—O—, —O—C(═O)—, X ２ is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms; n is 0, Z ２ are each independently an alkyl group having 1 to 3 carbon atoms, The polymer (A) contains repeating units derived from the silicon-containing monomer in an amount of 97% by weight or more based on the weight of the polymer (A), and The number average molecular weight of the polymer (A) is 100,000 or more and 2,000,000 or less, The water repellent composition according to claim 1, wherein the dispersant (B) is a cationic dispersant. A method for producing a textile product, comprising applying the water repellent composition according to any one of claims 1 to 14 to a textile substrate. Before applying the water repellent composition to the fiber substrate, -SO ３ M １ (In the formula, M １ represents a monovalent cation), -COOM 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. A textile product comprising a textile substrate to which the water repellent composition according to any one of claims 1 to 14 is attached. -SO ３ M １ (In the formula, M １ represents a monovalent cation), -COOM 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.

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