Water-repellent composition

Abstract

The present invention provides a water-repellent composition capable of imparting both good water repellency and good slip resistance to a substrate (especially textile products). [Solution] The following formula: CH2=C(-R a )-X-SiZ3 [where: R a is H or a hydrocarbon group having 1 to 5 carbon atoms, and X is X 1 and X 2 A divalent group consisting of one or more selected from the group, X 1 X is a group composed of one or more selected from the group consisting of -O-, -C(=O)-, and -NR'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), 2 A water-repellent composition comprising a polymer (A) containing repeating units derived from a silicon-containing monomer represented by ], wherein polymer (A) contains 90% by weight or more of the repeating units derived from the silicon-containing monomer, and the number-average molecular weight of polymer (A) is 60,000 or more and 4,000,000 or less.

Description

[Technical Field]

[0001] This disclosure relates to a water-repellent composition. [Background technology]

[0002] Development of non-fluorine-based water repellents is underway to impart water repellency to base materials (especially textile products). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Chinese Patent No. 116289217 Specification [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] When conventional water-repellent agents are used on textile products, there is a risk that the seams may slip, reducing the reliability of the textile product.

[0005] The present disclosure aims to provide a water-repellent composition that can impart both good water repellency and good slip resistance to textile products. [Means for solving the problem]

[0006] This disclosure includes the following aspects: [Section 1] The following formula: CH2=C(-R a )-X-SiZ3 [In formula: R a This is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. X is X 1 and X 2 A divalent group consisting of one or more selected from the group comprising, X 1is a group composed of one or more selected from the group consisting of -O-, -C(=O)-, and -NR'-(where R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms in each occurrence). X 2 is a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms. Z is independently a hydrocarbon group having 1 to 10 carbon atoms or -(O-SiZ 1 2) n -O-SiZ 2 3, Z 1 is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 11 3, Z 11 is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 111 3, Z 111 is independently a hydrocarbon group having 1 to 10 carbon atoms. Z 2 is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 21 3, Z 21 is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 211 3, Z 211 is independently a hydrocarbon group having 1 to 10 carbon atoms. n is independently an integer from 0 to 196.] A polymer (A) containing repeating units derived from a silicon-containing monomer represented by and a dispersant (B), The polymer (A) contains 90% by weight or more of the amount of repeating units derived from the silicon-containing monomer in 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, a water repellent composition. [Item 2] X is -X 1 -X 2 -[[]] [wherein, X 1These are -C(=O)-O-, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, or -C(=O)-NR'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms in each occurrence). X 2 It is a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms. A water-repellent composition according to item 1, wherein the group is represented by . [Section 3] Z 1 These are, independently, -OSiZ 11 3, Z 11 Each of these is independently an alkyl group having 1 to 3 carbon atoms. Z 2 These are, independently, -OSiZ 21 3, Z 21 The water-repellent composition according to item 1 or 2, wherein each of them is an alkyl group having 1 to 3 carbon atoms. [Section 4] 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. [Section 5] A water-repellent composition according to any one of items 1 to 4, wherein n is 0. [Section 6] The water-repellent composition according to any one of claims 1 to 5, wherein the polymer (A) contains 96% by weight or more of repeating units derived from the silicon-containing monomer of the weight of the polymer (A). [Section 7] A water-repellent composition according to any one of claims 1 to 6, wherein the number average molecular weight of the polymer (A) is 2,000,000 or less. [Section 8] The dispersant (B) is a water-repellent composition according to any one of claims 1 to 7, comprising a cationic dispersant. [Section 9] A 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. [Section 10] The water-repellent composition according to claim 9, wherein the amount of polymer (A) in the water-repellent composition is 5% to 95% by weight of the sum of the amount of polymer (A) and the amount of compound (C). [Section 11] The water-repellent composition according to claim 9 or 10, wherein the compound (C) is a polymer comprising repeating units derived from a hydrocarbon group-containing monomer having a hydrocarbon group having 2 to 40 carbon atoms. [Section 12] The hydrocarbon group-containing monomer is of the following formula: CH2=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 These are directly bonded, 2-4 valent C1 hydrocarbon groups, -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2-, and -NR C1 -(R C1 This is a 2-4 valent group composed of at least one selected from a hydrogen atom or a hydrocarbon group having 1-4 carbon atoms. k is 1 to 3, R d These are, independently, hydrocarbon groups having 2 to 40 carbon atoms. The water-repellent composition described in item 11, which is a monomer represented by . [Section 13] X is -X 1 -X 2 - [In the formula, X 1These are -C(=O)-O-, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, or -C(=O)-NR'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms in each occurrence). X 2 It is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms. It is a group represented by ] n is 0, Z 2 Each of these is independently an alkyl group having 1 to 3 carbon atoms. The following formula: CH2=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 These are directly bonded, 2-4 valent C1 hydrocarbon groups, -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2-, and -NR C1 -(R C1 This is a 2-4 valent group composed of at least one selected from a hydrogen atom or a hydrocarbon group having 1-4 carbon atoms. k is 1 to 3, R d It is a hydrocarbon group with 2 to 40 carbon atoms. The compound (C) further comprises a polymer containing repeating units derived from a hydrocarbon group-containing monomer represented by , The water-repellent composition according to claim 1, wherein the amount of polymer (A) in the water-repellent composition is 5% by weight to 95% by weight of the sum of the amount of polymer (A) and the amount of compound (C). [Section 14] 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- or -O-C(=O)-, X 2 is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, n is 0, Z 2 is each independently an alkyl group having 1 to 3 carbon atoms, The polymer (A) contains 97% by weight or more of the amount of repeating units derived from the silicon-containing monomer in 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, A water repellent composition according to any one of items 1 to 13, wherein the dispersant (B) is a cationic dispersant. [Item 15] A method for producing a fiber product, which includes applying a water repellent composition according to any one of items 1 to 14 to a fiber substrate. [Item 16] Before applying the water repellent composition to the fiber substrate, the fiber is -SO3M 1 (wherein M 1 represents a monovalent cation) a monovalent group represented by, -COOM 2 (wherein M 2 represents a monovalent cation) a monovalent group represented by, and -O-P(O)(OX 1 )(OX 2 (wherein X 1 and X 2 each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) a method for producing a fiber product according to item 15, which includes a step of imparting one or more functional groups selected from the group consisting of monovalent groups represented by. [Item 17] A fiber product to which a water repellent composition according to any one of items 1 to 13 is attached to a fiber substrate. [Item 18] -SO3M 1 (wherein M 1 represents a monovalent cation) a monovalent group represented by, -COOM2 (In the formula, M 2 (where represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 The textile product according to item 17, to which a compound having one or more functional groups selected from the group consisting of monovalent groups (each independently representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) is attached. [Effects of the Invention]

[0007] The water-repellent compositions in this disclosure can impart both good water repellency and good slip resistance to substrates (especially textile products). [Modes for carrying out the invention]

[0008] <Definition of Terms> As used herein, "n-valent group" means a group having n bonds, that is, a group that forms n bonds. Furthermore, "n-valent organic group" means an n-valent group containing carbon, and "organic group" means a group containing carbon. Such organic groups are not particularly limited, but may be hydrocarbon groups or derivatives thereof. A derivative of a hydrocarbon group means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the terminal or molecular chain of a hydrocarbon group.

[0009] As used herein, "hydrocarbon group" means a group containing carbon and hydrogen, obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups are not particularly limited, but include C 1-20 The hydrocarbon group may be, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, etc. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents.

[0010] In this specification, unless otherwise stated, whether or not the phrase "independently in each instance," "independently," or similar expressions are explicitly stated, if a term (symbol) that may appear multiple times in a chemical structure is defined, the definition shall apply independently to each instance.

[0011] The chemical structures described herein should be understood to exclude any chemical structures that would be considered chemically impossible or extremely unstable by those skilled in the art.

[0012] <Water-repellent composition> Water-repellent compositions in this disclosure, The following formula: CH2=C(-R a )-X-SiZ3 [In formula: R a This is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. X is X 1 and X 2 A divalent group consisting of one or more selected from the group comprising, X 1 This is a group composed of one or more elements selected from the group consisting of -O-, -C(=O)-, and -NR'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms in each instance). X 2 It is a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms. Z is independently a hydrocarbon group having 1 to 10 carbon atoms or -(O-SiZ 1 2) n -O-SiZ 2 3, Z 1 Each of these is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 11 3, Z 11 Each of these is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 111 3, Z111 is independently a hydrocarbon group having 1 to 10 carbon atoms, Z 2 is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 21 3, Z 21 is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 211 3, Z 211 is independently a hydrocarbon group having 1 to 10 carbon atoms, n is independently an integer from 0 to 196.] The water repellent composition of the present disclosure contains a polymer (A) containing a repeating unit derived from a silicon-containing monomer represented by the formula and a dispersant (B). The polymer (A) contains 90% by weight or more of the silicon-containing monomer in 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] Due to having the above characteristics, the water repellent composition in the present disclosure can impart liquid repellency (water repellency, oil repellency, oil resistance, and / or water resistance) to a substrate (for example, a fiber substrate, a paper substrate). The polymer (A) of 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 in the present disclosure can impart good oil resistance (oil repellency) and / or water resistance (water repellency) to a substrate, and can, for example, impart both good oil resistance and water resistance.

[0014] Due to having the above characteristics, the water repellent composition in the present disclosure can adhere to a substrate (for example, a fiber substrate, a paper substrate) and 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 repeating units derived from a silicon-containing monomer. The polymer (A) is a polymer formed by polymerizing monomers. Here, 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, vinylene group, vinylidene group, acryloyl group, methacryloyl group, or a derivative group thereof.

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

[0017] The polymer (A) of the present disclosure may be non-fluorine-based. 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 repeating units derived from a silicon-containing monomer. The silicon-containing monomer is represented by the following formula. CH2=C(-R a )-X-SiZ3

[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, and may be a methyl group. Among them, R a is preferably a hydrogen atom or a methyl group.

[0020] [X] X is a divalent group composed of one or more selected from the group consisting of X 1 and X 2 , and X 1 ​This is a group composed of one or more elements selected from the group consisting of -O-, -C(=O)-, and -NR'- (wherein R' 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) in each instance). X 2 It 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 It is a non-hydrocarbon linker.

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

[0024] X 1 This is a group composed of one or more elements selected from the group consisting of -O-, -C(=O)-, and -NR'- (wherein R' 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) in each instance).

[0025] X 1 Examples include, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, Examples include -C(=O)-NR'-, etc. In the formula, R' 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) in each instance.

[0026] In one embodiment, X 1 teeth, It may be -C(=O)-O- or -C(=O)-NR'-, where R' may independently be a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms in each instance.

[0027] (X 2 ) X 2 This is a hydrocarbon group that may be directly bonded or have substituents. 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 also 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 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 embodiment, X 2 The number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, or 3 or more, and may be 6 or less, 5 or less, or 4 or less.

[0031] In one embodiment, X 2 This 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 2 The hydrocarbon group in may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (wherein R' 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 in each occurrence). The substituents 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.

[0033] X 2 A specific example is -(CH2) q - are examples. q is an integer between 1 and 22. q may be 1 or greater, 2 or greater, 3 or greater, 4 or greater, 5 or greater, 7 or greater, 9 or greater, 11 or greater, or 13 or greater. 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.

[0034] (Example of X) An example of X is -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. A preferred example of X is -X 1 -X 2 -, -X 2 - are listed.

[0035] In one embodiment, X is -X1 -X 2 - [In the formula, X 1 These are -C(=O)-O-, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, or -C(=O)-NR'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms in each occurrence). X 2 This 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. It is a base represented by .

[0036] In one embodiment, X is -C(=O)-O-(CH2) q -or -C(=O)-NR'-(CH2) q - may be, and R' may independently be a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms in each occurrence, and q may be 1 or more, 2 or more, or 3 or more, and may also be 6 or less, 5 or less, 4 or less, or 3 or less.

[0037] [Z] Z is a group that bonds to Si in silicon-containing monomers.

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

[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, Z is independently -(O-SiZ 1 2) n-O-SiZ 2 It can be 3.

[0041] (Z 1 ) Z 1 Each of these is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 11 The answer is 3.

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

[0043] In one embodiment, Z 1 This may be a methyl group or an ethyl group, and is preferably a methyl group.

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

[0045] (Z 11 ) Z 11 Each of these is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 111 The answer is 3.

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

[0047] In one embodiment, Z 11 This may be a methyl group or an ethyl group, and is preferably a methyl group.

[0048] Above -OSiZ11 Three Zs in 3 11 These may all be hydrocarbon groups having 1 to 10 carbon atoms, or all may be -OSiZ 111 It may be 3, or two hydrocarbon groups having 1 to 10 carbon atoms and -OSiZ 111 It may be one 3, or one hydrocarbon group having 1 to 10 carbon atoms and -OSiZ 111 It is acceptable to have two 3s.

[0049] (Z 111 ) Z 111 Each of these is independently a hydrocarbon group having 1 to 10 carbon atoms.

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

[0051] In one embodiment, Z 111 This may be a methyl group or an ethyl group, and is preferably a methyl group.

[0052] (Z 2 ) Z 2 Each of these is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 21 The answer is 3.

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

[0054] In one embodiment, Z 2 This may be a methyl group or an ethyl group, and is preferably a methyl group.

[0055] The above OSiZ 2 Three Zs in 3 2These may all be hydrocarbon groups having 1 to 10 carbon atoms, or all may be -OSiZ 21 It may be 3, or two hydrocarbon groups having 1 to 10 carbon atoms and -OSiZ 21 It may be one 3, or one hydrocarbon group having 1 to 10 carbon atoms and -OSiZ 21 It is acceptable to have two 3s.

[0056] (Z 21 ) Z 21 Each of these is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 211 The answer is 3.

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

[0058] In one embodiment, Z 21 This may be a methyl group or an ethyl group, and is preferably a methyl group.

[0059] Above -OSiZ 21 Three Zs in 3 21 These may all be hydrocarbon groups having 1 to 10 carbon atoms, or all may be -OSiZ 211 It may be 3, or two hydrocarbon groups having 1 to 10 carbon atoms and -OSiZ 211 It may be one 3, or one hydrocarbon group having 1 to 10 carbon atoms and -OSiZ 211 It is acceptable to have two 3s.

[0060] (Z 211 ) Z 211 Each of these is independently a hydrocarbon group having 1 to 10 carbon atoms.

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

[0062] In one embodiment, Z 211 This may be a methyl group or an ethyl group, and is preferably a methyl group.

[0063] (Example of Z) Z in one aspect of Z 1 and Z 2 Regarding Z 1 These are, independently, -OSiZ 11 3, Z 11 Each of these is independently an alkyl group having 1 to 3 carbon atoms. Z 2 These are, independently, -OSiZ 21 3, Z 21 Each of these is an alkyl group having 1 to 3 carbon atoms, independently of the others.

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

[0065] In one embodiment, n for at least one Z in -SiZ3 may be 0, n for at least two Zs may be 0, or n for all Zs may be 0.

[0066] [Examples of silicon-containing monomers] An example of a silicon-containing monomer is the following formula: CH2=C(-R a )-X 1 -(CH2) q -Si(-O-SiZ 2 3)3 [In formula: R a This is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. X 1 This is a group composed of one or more elements selected from the group consisting of -O-, -C(=O)-, and -NR'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms in each instance). q is an integer between 1 and 22. Z 2 Each of these is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 21 3, Z 21 These are, independently, hydrocarbon groups having 1 to 10 carbon atoms. Examples of silicon-containing monomers represented by [formula] include [formula].

[0067] In the above example, R a This 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 a methyl group.

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

[0069] In the above example, q may be 1 or greater, 2 or greater, 3 or greater, 4 or greater, 5 or greater, 7 or greater, 9 or greater, 11 or greater, or 13 or greater. q may also 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 Each of these is independently a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 21 It is 3. Z 2 This is preferably a hydrocarbon group having 1 to 10 carbon atoms.

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

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

[0073] [Number average molecular weight] The number-average molecular weight of polymer (A) is between 60,000 and 4,000,000. The number-average molecular weight of 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, and also 400,000 The number average molecular weight may be 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 polymer (A) may be 70,000 or more and 1,800,000 or less, preferably 70,000 or more and 700,000 or less, 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 (on a polystyrene basis). For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (manufactured by Tosoh Corporation) was used. Three TSKgel SuperMultiporeHZ-M columns were connected together. An RI detector was used. Standard polystyrene (SRM706a NIST) was used as the standard material. For the analysis sample, polymer components were recovered by reprecipitation using IPA as a poor solvent, dissolved in tetrahydrofuran to make a 0.1% by weight solution, and passed 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, and 100 μL of the analysis sample was injected at a flow rate of 0.35 mL / min.

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

[0076] [Composition of polymer (A)] Polymer (A) contains 90% or more by weight of repeating units derived from silicon-containing monomers. The amount of repeating units derived from the silicon-containing monomer 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, and may be 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. Furthermore, if the amount of repeating units derived from the silicon-containing monomer is 100% by weight relative to polymer (A), it means that polymer (A) is a homopolymer of silicon-containing monomers (in other words, a homopolymer of silicon-containing monomers).

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

[0078] In one embodiment, the polymer (A) of the present disclosure may include repeating units derived from a silicon-containing monomer and repeating units derived from a hydrocarbon group-containing monomer (a). A preferred example of such hydrocarbon group-containing monomer (a) is provided by reference to the description of hydrocarbon group-containing monomer (a) in the description of compound (C) below.

[0079] The amount of repeating units derived from the above-mentioned 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 relative to polymer (A), and may also 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. In one embodiment, polymer (A) of the present disclosure may not contain the above-mentioned other monomers.

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

[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, based on 100 parts by weight of the total amount of polymer (A), dispersant (B), and compound (C), or 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, based on 100 parts by weight of the total amount of polymer (A), dispersant (B), and compound (C). In one embodiment, the preferred amount of polymer (A) is 8 to 90 parts by weight per 100 parts by weight of the total amount of polymer (A), dispersant (B), and compound (C).

[0082] [Polymerization method] Polymer (A) can be produced by known polymerization methods, and the conditions for the polymerization reaction can be arbitrarily selected. 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 monomers from monomers (a) to (h) exemplified by compound (C), which will be described in detail below, with a silicon-containing monomer.

[0084] In solution polymerization, a silicon-containing monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen purging, the mixture is heated and stirred at a temperature 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 monomer.

[0085] Organic solvents are inert to silicon-containing monomers and dissolve them. Examples include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone, and methyl isobutyl ketone), and alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically ethanol, butanol, and 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 3000 parts by weight, for example, 50 to 2000 parts by weight, per 100 parts by weight of the total silicon-containing monomers.

[0086] In emulsion polymerization, a method is employed in which silicon-containing monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, followed by nitrogen purging, heating to a predetermined temperature, and stirring to induce polymerization.

[0087] The proportion of emulsifier added 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, per 100 parts by weight of the total amount of monomer, or 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 proportion of water used in the mixture 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, per 100 parts by weight of the total amount of monomer, or it 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.

[0089] Polymerization initiators include water-soluble ones 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 ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate.

[0090] The proportion of polymerization initiator may be, for example, 0.01 parts by weight or more, and for example, 10 parts by weight or less, per 100 parts by weight of monomer.

[0091] Various emulsifiers, including anionic, cationic, and nonionic types, can be used as emulsifiers, and are used in an amount ranging from 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. Known emulsifiers can be used as emulsifiers, and dispersants exemplified by dispersant (B) described below can also be used. Emulsifiers can be used alone or in combination of two or more types.

[0092] As a method of stirring, dispersants such as homomixers, ultrasonic homogenizers, pressurized homogenizers, milders, and porous membrane injection dispersers can be used, and preferably a homomixer is used. Stirring makes it easier to obtain an aqueous polymer dispersion with excellent standing stability.

[0093] The stirring conditions are set as appropriate. When using a homomixer, 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 miscible, it is preferable to add a compatibilizer that makes them sufficiently miscible, such as a water-soluble organic solvent or a low molecular weight monomer. Adding a compatibilizer can improve emulsifying and copolymerizing properties.

[0095] As the water-soluble organic solvent, the organic solvents mentioned above may be used. For example, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc., may be used in a range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. In addition, as low molecular weight monomers, methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., may be used in a range 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] In polymerization, a chain transfer agent may be used. 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 (especially alkyl mercaptans (e.g., with 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. 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 monomer.

[0097] In polymerization, an organic acid may be added. For example, the organic acid may be an organic acid of this disclosure, or a carboxylic acid such as acetic acid. The amount of 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, or 0.5 parts by weight or less, per 100 parts by weight of the total amount of monomers.

[0098] Polymerization conditions may include a heating temperature of, for example, 40°C or higher, or 80°C or lower, and a heating time of, for example, 1 hour or more, or 6 hours or less.

[0099] By following the process described above, polymer (A) can be obtained. In the case of emulsion polymerization, an emulsion containing polymer (A) and dispersant (B) can be obtained.

[0100] [(B) Dispersant] The water-repellent composition in this disclosure comprises 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 in this disclosure may contain a nonionic dispersant, or a combination of a nonionic dispersant and a cationic dispersant. By including a dispersant (B), good water repellency, slip resistance, and storage stability can be achieved.

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

[0102] An organic dispersant may be used as the dispersant (B). Organic dispersants can be classified into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants, and the term "organic dispersant" may refer to a surfactant.

[0103] The dispersant (B) does not need to contain fluorine atoms.

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

[0105] The nonionic dispersant may be of low molecular weight (e.g., molecular weight 2000 or less, particularly 10000 or less) or high molecular weight (e.g., molecular weight 2000 or more). The molecular weight of the nonionic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 7500000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 100000 or less, 7500 or less, 50000 or less, 2500 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] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0108] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1-30 valencies (especially 2-10 valencies) with 1-50 carbon atoms (especially 10-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0109] Examples of ester ethers are compounds formed by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are 1-30 valencies (especially 2-10 valencies) with 1-50 carbon atoms (especially 3-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0110] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolamides. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0111] The polyol may be a divalent to pentavalent alcohol with 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (a secondary amine or preferably a tertiary amine) (for example, having 5 to 50 carbon atoms).

[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 of 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 linear and / or branched aliphatic (saturated and / or unsaturated) groups, a polyalkylene glycol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a sorbitan ester of linear and / or branched fatty acids (saturated and / or unsaturated), a glycerol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a polyglycerol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a sucrose ester of linear and / or branched fatty acids (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, etc. Among these, those in which the alkylene oxide addition portion and the polyalkylene glycol portion have structures of polyoxyethylene (POE), polyoxypropylene (POP), or POE / POP copolymer (which may be random copolymer or block copolymer) are preferred. Furthermore, the nonionic dispersant does not need to contain aromatic groups.

[0115] The nonionic dispersant is, formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 This is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms. R 2 Each of these is independently identical or distinct, an alkylene group having 3 or more carbon atoms (e.g., 3 to 10). R 3 These are 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 greater than or equal to 2. q is a number greater than or equal to 1, or 0. It may be a compound represented by [the formula shown].

[0116] R 1The carbon atoms have 8 to 20 carbon atoms, and are more preferably 10 to 18 carbon atoms. 1 Preferred specific examples include the octyl group, nonyl group, trimethylnonyl group, lauryl group, tridecyl group, oleyl group, and stearyl group. R 2 Examples include the propylene group and the butylene group. In nonionic dispersants, p may be a number greater than or equal to 3 (e.g., 5 to 200). q may be a number greater than or equal to 2 (e.g., 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, but oxypropylene chains are preferred among these.

[0117] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, and alkanes (C 12 -C 16 ) Thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl(C 12 -C 18 This includes condensation products with amines, 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 especially 40 to 70% by weight, relative to the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of nonionic dispersants 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 compounds with an HLB (hydrophilic-hydrophobic balance) of 10 or less, and may be a mixture of compounds with an HLB of less than 15 (especially 5 or less) and compounds with an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene with HLB values ​​of 1 to 18, or 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 with HLB values ​​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 that does not have an amide group.

[0120] The cationic dispersant may be of low molecular weight (e.g., molecular weight 2000 or less, particularly 10000 or less) or high molecular weight (e.g., molecular weight 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 7500000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 100000 or less, 7500 or less, 50000 or less, 2500 or less, 750 or less, or 250 or less.

[0121] Cationic dispersants may be aliphatic or aromatic, such as ammonium salts (e.g., quaternary ammonium salts). Cationic dispersants may also be oxyethylene-added ammonium salts. Specifically, examples include amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymeric cationic dispersants such as polyquaternium-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0122] Low molecular weight cationic dispersants are 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. X is an anionic group. It may be a compound represented by R. 21 , R 22 , R 23 and R 24 Specific examples of X include alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group) and aromatic groups (e.g., benzyl group, phenyl group). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid, acetic acid). Examples of cationic dispersants include monoalkyltrimethylammonium salts (alkyl group with 4 to 40 carbon atoms) and benzalkonium chloride.

[0123] Specifically, low-molecular-weight cationic dispersants have the formula: R 1 p -N +R 2 q X - [In the formula, R 1 is C12 or higher (for example, C 12 ~C 50 ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group, R 2 The elements are H or C1-C4 alkyl groups, benzyl groups, and polyoxyethylene groups (number of oxyethylene groups, for example, 1 (particularly 2, especially 3) to 50) (CH3 and C2H5 are particularly preferred). X is a halogen atom (e.g., chlorine), or a C1-C4 fatty acid salt, or a C1-C4 sulfonate. p is either 1 or 2, q is either 2 or 3, and p + q = 4. It may be an ammonium salt represented by R. 1 The number of carbon atoms can be 12 to 50, for example, 12 to 30.

[0124] Low molecular weight cationic dispersants may 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, etc.

[0125] The polymeric cationic dispersant may be various polymers (e.g., polyquaternium-1 to 47) having cationic groups (e.g., ammonium groups, quaternary ammonium groups). Examples of polymeric cationic dispersants include cationized starch, cationized cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationized guar gum, cationized xanthan gum, chitosan, and other cationized natural products (especially cationized sugars); 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 methacrylic acid, 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 does not have to contain an anionic dispersant.

[0127] The anionic dispersant may be of low molecular weight (e.g., molecular weight of 2000 or less, particularly 10000 or less) or of high molecular weight (e.g., molecular weight of 2000 or more). The molecular weight of the anionic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 7500000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 100000 or less, 7500 or less, 50000 or less, 2500 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-sulfone fatty acid salts, N-acyl amino acid type dispersants, phosphate mono or diester type dispersants, and sulfosuccinate esters. An example of anionic dispersants is a carboxylate salt (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 of low molecular weight (e.g., molecular weight 2000 or less, especially 10000 or less) or high molecular weight (e.g., molecular weight 2000 or more). The molecular weight of the amphoteric dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 7500000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 100000 or less, 7500 or less, 50000 or less, 2500 or less, 750 or less, or 250 or less.

[0131] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, these include lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

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

[0133] The average primary particle size of the inorganic dispersant may be 5 nm or larger, 30 nm or larger, 100 nm or larger, 1 μm or larger, 10 μm or larger, or 25 μm or larger, and may also be 100 μm or smaller, 50 μm or smaller, 10 μm or smaller, 1 μm or smaller, 500 nm or smaller, or 300 nm or smaller. 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 also 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, per 100 parts by weight of polymer (A), and may also 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, the preferred amount of dispersant (B) is 5 to 20 parts by weight per 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, based on 100 parts by weight of the total amount of polymer (A) and compound (C), or it 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, the preferred amount of dispersant (B) is 5 to 20 parts by weight per 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, based on 100 parts by weight of the total amount of polymer (A), dispersant (B), and compound (C), and may also 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, the preferred amount of polymer (A) is 6 to 15 parts by weight per 100 parts by weight of the total amount of polymer (A), dispersant (B), and compound (C).

[0138] [(C) compound] The water-repellent compositions of the present disclosure may further contain compound (C) as described below. Preferably, the water-repellent compositions of the present disclosure contain at least one compound (C) selected from the group consisting of vinyl polymers, isocyanate derivatives, waxes, and silicones.

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

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

[0141] Vinyl polymers are polymers obtained by polymerizing vinyl monomers. Here, the monomers can be any compound having a polymerizable carbon-carbon double bond (ethylenically unsaturated double bond) (>C=C<), and may be monomers containing a vinyl group, vinylene group, vinylidene group, acryloyl group, methacryloyl group, or derivative groups thereof.

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

[0143] The vinyl polymer is preferably a compound having bio-based carbon. The degree of biobase is measured in accordance with ASTM D6866. The degree of biobase 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 degree of biobase means that the amount of fossil resource-based materials, such as petroleum, used is small, and from this viewpoint, a higher degree of biobase of the vinyl polymer is preferable.

[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 also 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 this disclosure does not necessarily have to have any of the following 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 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 5000000 or less, 3000000 or less, 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, or 5000 or less. The weight-average molecular weight may be the polystyrene-equivalent molecular weight measured by GPC.

[0147] (a) hydrocarbon group-containing monomers The vinyl polymers of this disclosure may have repeating units derived from a hydrocarbon group-containing monomer (a). Monomer (a) has one ethylenically unsaturated double bond and a hydrocarbon group having 2 to 40 carbon atoms.

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

[0149] (Hydroxide group with 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 substituents, but it is preferable that it does not. Here, the hydrocarbon group is a monovalent group.

[0150] The hydrocarbon group of monomer (a) may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched or linear, and is more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group).

[0151] Hydrocarbon groups are typically monovalent and may be located at the end of the molecule, and may have one or more methyl groups at the end of the hydrocarbon group. In this specification, hydrocarbon compounds (e.g., hydrocarbon waxes) are understood to consist only of a monovalent hydrocarbon group and one hydrogen atom, and for example, a C20 n-alkane (eicosane) is understood to consist only of a C20 alkyl group 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 also 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 substituents, but it is preferable that it be unsubstituted. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (wherein R' 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 in each occurrence). The substituents 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 a hydrocarbon group having substituents, 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 also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, a hydrocarbon group may have 1 to 3 (e.g., 1) -OR' (especially -OH) substituents (e.g., not at the terminal ends).

[0154] The hydrocarbon group-containing monomer (a) is given by the following formula: CH2=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 These are divalent to tetravalent carbon-1 hydrocarbon groups (especially -CH2-, -CH(-)2), -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2-, and -NR C1 -(R C1 This is a group composed of at least one selected from a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. k is 1 to 3, R d These are, independently, hydrocarbon groups having 2 to 40 carbon atoms. It is preferable that the monomer is represented by .

[0155] R b R may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. b Examples include hydrogen atoms, methyl groups, chlorine atoms, bromine atoms, iodine atoms, and cyano groups. b It is preferable that R is a hydrogen atom, a methyl group, or a chlorine atom. b It is particularly preferable that it be a hydrogen atom.

[0156] R c It is a divalent to tetravalent group. a It is preferable that the group is divalent. R c It is preferable that the group is composed of at least one of the following: a hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH-. a It is preferable that it is not a hydrocarbon group. Examples of a C1 hydrocarbon group include -CH2-, -CH(-)2, or -C(-)3. A hydrocarbon group having C1 is repeated, and -(CH2) m -(m is an integer from 1 to 5) may form a hydrocarbon group with 2 or more carbon atoms. a It may 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'- [In the formula, R c ' is a direct bond, -O-, -NH- or -S(=O)2-, R' is -(CH2) m -(m is an integer between 1 and 5) or -C6H4- (phenylene group). That's fine.

[0158] R c Specific examples are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m-OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4-, -NH-(CH2) m -NH-S(=O)2-, or -NH-(CH2) m The formula is -S(=O)2-NH- [wherein m is 1 to 5, especially 2 or 4].

[0159] R c -O-, -NH-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2-, or -NH-(CH2) m -S(=O)2-NH- [In the formula, m is an integer between 1 and 5, in particular 2 or 4.] It is preferable that this is the case.a is -O- or -O-(CH2) m -NH-C(=O)-, especially -O-(CH2) m -NH-C(=O)- is more preferable.

[0160] R d Each of these is independently a hydrocarbon group having 2 to 40 carbon atoms, and, referring to the previously described content of (hydrocarbon groups having 2 to 40 carbon atoms) above, it is preferable that they are linear or branched hydrocarbon groups. The hydrocarbon group may be a linear hydrocarbon group in particular. The hydrocarbon group is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, and especially an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example, 12 to 18, 16 to 26, or 15 to 26, and especially 18 to 22 or 17 to 22.

[0161] A concrete example of monomer (a) is: Formula (a1): CH2=C(-X a1 )-C(=O)-Y a11 -Z(-Y a12 -R a1 ) n [In the formula, R a1 Each of these is independently a hydrocarbon group having 2 to 40 carbon atoms. X a1 is a hydrogen atom, a monovalent organic group, or a halogen atom. Y a11 is -O- or -NH-, Y a12 Each of these groups is independently composed of a direct bond or at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-. Z is a directly bonded or divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms. n is either 1 or 2. A monomer represented by, and Formula (a2): CH2=C(-X a2 )-C(=O)-Y a2 -Ra2 [In the formula, R a2 This is a hydrocarbon group having 2 to 40 carbon atoms. X a2 is a hydrogen atom, a monovalent organic group, or a halogen atom. Y a2 It is -O- or -NH-. monomer represented by That is the case.

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

[0163] Monomer (a1) may be a monomer having a hydrocarbon group having 2 to 40 carbon atoms and an NH group-containing group. 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 monomer may be a combination of a hydrocarbon monomer having an amide group, a urea group, a urethane group, or a sulfonamide group and a hydrocarbon monomer not having an amide group, a urea group, a urethane group, or a sulfonamide group. The effects of this disclosure can be well achieved by including such groups in monomer (a1).

[0164] Monomer (a1) is a (meth)acrylate or (meth)acrylamide having a group composed of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-.

[0165] The monomer (a1) is given by the formula: CH2=C(-X a1 )-C(=O)-Y a11 -Z(-Y a12 -R a1 ) n [In the formula, R a1 Each of these is independently a hydrocarbon group having 2 to 40 carbon atoms. X a1 is a hydrogen atom, a monovalent organic group, or a halogen atom. Y a11 is -O- or -NH-, Y a12 Each of these groups is independently composed of a direct bond or at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-. Z is a directly bonded or divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms. n is either 1 or 2. It may be a compound represented by Y. a12 And / or Z does not have to be directly connected. a12 And Z do not necessarily have to be directly bonded at the same time.

[0166] R a1 It is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. a1 In this, the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22.

[0167] X a1 This may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. A hydrogen atom, a methyl group, or a chlorine atom is preferred.

[0168] Y a12 -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, Y' is independently a direct bond, -O-, -NH-, or -S(=O)2-, R' is -(CH2) m -(m is an integer from 1 to 5), a linear hydrocarbon group having an unsaturated bond with 1 to 5 carbon atoms, a branched hydrocarbon group having 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2)l -(where l is an independent integer between 0 and 5, and -C6H4- is a phenylene group). That's fine.

[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-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4- [In the formula, m is an integer between 1 and 5.] That is the case.

[0170] Especially Y a12 It may have an NH group.

[0171] Y a12 is preferably -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-, -O-C6H4-. Y a12 It is more preferable that -NH-C(=O)-, -C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, or -NH-C(=O)-NH-. a12 The bond does not have to be a direct one.

[0172] Z is a directly bonded, or divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a linear or branched structure. The number of carbon atoms in Z is preferably 2 to 4, particularly 2. Specific examples of Z are directly bonded, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH(-)2, -CH2(CH-)CH2-, -CH2CH2CH(-)2, -CH2CH2(CH-)CH2-, -CH2CH2CH2CH(-)2. Z does not have to be directly bonded.

[0173] The monomer (a1) is CH2=C(-X a1 )-C(=O)-O-(CH2) m -NH-C(=O)-R a1 CH2=C(-X a1 )-C(=O)-O-(CH2) m -OC(=O)-NH-R a1 CH2=C(-X a1 )-C(=O)-O-(CH2) m -NH-C(=O)-OR a1 CH2=C(-X a1 )-C(=O)-O-(CH2) m-NH-C(=O)-NH-R a1 It is preferable that R a1 and X a1 This is synonymous with the above. The monomer (a1) is CH2=C(-X a1 )-C(=O)-O-(CH2) m -NH-C(=O)-R a1 It is particularly preferable that this be the case.

[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 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] A preferred example of monomer (a) is as follows: Stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, behenyl α-chloroacrylate; Stearyl(meth)acrylamide, behenyl(meth)acrylamide;

[0176] JPEG0007846437000001.jpg2554

[0177] JPEG0007846437000002.jpg7556

[0178] JPEG0007846437000003.jpg7758

[0179] JPEG0007846437000004.jpg10460

[0180] JPEG0007846437000005.jpg2147

[0181] JPEG0007846437000006.jpg2350 [In the above formula, n is a number between 6 and 40, and m is a number between 1 and 5.] The compound with the above chemical formula is an acrylic compound in which the α-position is a hydrogen atom, but specific examples may include methacrylic compounds in which the α-position is a methyl group and α-chloroacrylic compounds in which the α-position is a chlorine atom.

[0182] The monomer (a1) is given by the formula: R a12 -C(=O)-NH-R a13 -OR a11 [In the formula, R a11 This is an organic residue having an ethylenically unsaturated polymerizable group. R a12 This is a hydrocarbon group having 2 to 40 carbon atoms. R a13 This is a hydrocarbon group having 1 to 5 carbon atoms. It is preferable that the monomer is an amide group-containing monomer represented by [formula].

[0183] R a11 This is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a polymer carbon carbon-carbon double bond. Specifically, -C(=O)CR a111 =CH2, -CHR a111 =CH2, -CH2CHR a111 Examples include organic residues having ethylenically unsaturated polymerizable groups such as CH2, and R a111Examples include hydrogen atoms or alkyl groups having 1 to 4 carbon atoms. Also, R a11 In addition to ethylenically unsaturated polymerizable groups, it may have various organic groups, such as 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 It is preferable that the formula is CH2.

[0184] R a12 As described above, monomer (a) has hydrocarbon groups, which are hydrocarbon groups having 2 to 40 carbon atoms, preferably alkyl groups, and include chain hydrocarbon groups, cyclic hydrocarbon groups, etc. Among these, chain hydrocarbon groups are preferred, and linear saturated hydrocarbon groups are particularly preferred. a12 The number of carbon atoms is 6 to 40, but preferably 11 to 27, and particularly preferably 15 to 23.

[0185] R a13 This 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 linear or branched, and may have unsaturated bonds, but linear is preferred. a13 The number of carbon atoms is preferably 2 to 4, and particularly preferably 2. a13 It is preferable that it is an alkylene group.

[0186] Amide group-containing monomers are R a12 Those that have only one type (for example, R a12 (Only compounds with 17 carbon atoms), or R a12 Those that are multiple combinations (for example, R a12 A compound with 17 carbon atoms and R a12 It may be a mixture of a compound having 15 carbon atoms.

[0187] An example of an amide group-containing monomer is carboxylic acid amide alkyl (meth)acrylate. Specific examples of amide group-containing monomers include palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, beheninic acid amidoethyl (meth)acrylate, myristateic acid amidoethyl (meth)acrylate, lauric acid amidoethyl (meth)acrylate, isostearate ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tert-butylcyclohexylcaproic acid amidoethyl (meth)acrylate, adamantane carboxylic acid ethyl amide (meth)acrylate, naphthalene carboxylic acid amidoethyl (meth)acrylate, anthracene carboxylic acid amidoethyl (meth)acrylate, palmitic acid amidopropyl (meth)acrylate, stearic acid amidopropyl (meth)acrylate, palmitic acid amidoethyl vinyl ether, stearic acid amidoethyl vinyl ether, palmitic acid amidoethyl allyl ether, stearic acid amidoethyl allyl ether, or mixtures thereof.

[0188] The amide group-containing monomer is preferably stearamide ethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamide ethyl (meth)acrylate. In a mixture containing stearamide ethyl (meth)acrylate, the amount of stearamide ethyl (meth)acrylate may be, for example, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight, and may be 90% or less by weight, 80% or less by weight, or 70% or less by weight, based on the total weight of the amide group-containing monomer. The remaining monomer may be, for example, palmitate ethyl (meth)acrylate.

[0189] (a2) monomer The monomer (a2) is given by the formula: CH2=C(-X a2 )-C(=O)-Y a2 -R a2 [In the formula, R a2 This is a hydrocarbon group having 2 to 40 carbon atoms. X a2is a hydrogen atom, a monovalent organic group, or a halogen atom. Y a2 It is -O- or -NH-. It is a compound represented by [formula].

[0190] The monomer (a2) is Y a2 A long-chain acrylate ester monomer in which is -O-, or Y a2 It is a long-chain acrylamide monomer with -NH-. R a2 It is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. a2 In this case, 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. X a2 This may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. A hydrogen atom, a methyl group, or a chlorine atom is preferred.

[0191] Preferred examples of long-chain acrylate ester monomers are 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 long-chain acrylamide monomers are stearyl(meth)acrylamide, eicosyl(meth)acrylamide, and behenyl(meth)acrylamide.

[0192] The vinyl polymers of this disclosure may include repeating units derived from the following monomers.

[0193] (b) Hydrophilic group-containing monomer The vinyl polymers of this disclosure may include repeating units derived from a hydrophilic group-containing monomer (b). Monomer (b) is a monomer other than monomer (a) that has a hydrophilic group.

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

[0195] The hydrophilic group is preferably an oxyalkylene-containing group (the alkylene group has 2 to 6 carbon atoms), and is particularly preferably an oxyethylene group. In particular, monomer (b) is preferably an oxyalkylene (meth)acrylate, such as 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) is, formula: CH2=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, Y b is -O- or -NH-, R b These are each an alkylene group having 2 to 6 carbon atoms, A b This is a hydrogen atom, an unsaturated or saturated hydrocarbon group with 1 to 22 carbon atoms, or CH2=CX b C(=O)- exists, n is an integer between 1 and 90. It is preferable that the oxyalkylene (meth)acrylate is represented by [formula].

[0197] An example of monomer (b) is given by formula: CH2=CX b C(=O)-O-(Rb O) n -A bi (b1) and CH2=CX b C(=O)-O-(R b O) n -C(=O)CX b =CH2(b2), CH2=CX b C(=O)-NH-(R b O) n -A bi (b3) [In the formula, X b Each of these is independently a hydrogen atom or a methyl group, A bi Each of these is independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms. R b These are each an alkylene group having 2 to 6 carbon atoms, n is an integer between 1 and 90. That is the case. It is preferable that it be represented by

[0198] n can be, for example, 1 to 50, especially 1 to 30, or more specifically 1 to 15 or 2 to 15. Alternatively, n can be, for example, 1. R b This may be a linear or branched alkylene group, for example, formula -(CH2) x - or - (CH2) x1 -(CH(CH3)) x2 -[In the formula, x1 and x2 are between 0 and 6, for example, between 2 and 5, and the sum of x1 and x2 is between 1 and 6. -(CH2) x1 -and-(CH(CH3)) x2 The order of the hyphens is not limited to the given formula and may be random. The base may be represented by ]. -(R b O) n -In this case, R may be of two or more types (for example, 2 to 4 types, especially 2 types), -(R b O) n - is, for example, -(R 1 O)n1 -and-(R 2 O) n2 -[wherein, R 1 and R 2 The combination may be: 1, n1 and n2 are mutually distinct 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 between 2 and 90.

[0199] R in equations (b1), (b2), and (b3) b R is particularly preferably an ethylene group, a propylene group, or a butylene group, especially a butylene group. b R may be a combination of two or more alkylene groups. In that case, it is preferable that at least one of R is an ethylene group, a propylene group, or a butylene group. b Examples of combinations include ethylene group / propylene group combinations, ethylene group / butylene group combinations, and propylene group / butylene group combinations. Monomer (b) may be a mixture of two or more types. In that case, at least one of monomer (b) is R in formula (b1), (b2), or (b3). b It is preferable that the group is an ethylene group, a propylene group, or a butylene group. Furthermore, when using polyalkylene glycol di(meth)acrylate represented by formula (b2), it is not preferable to use it alone as monomer (b), but rather to use it in combination with monomer (b1). In that case as well, it is preferable that the compound represented by formula (b2) be kept to less than 30% by weight of the monomer (b) used.

[0200] Specific examples of 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)O-H CH2=CH-C(=O)-NH-CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH(CH3)O-H 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-CH(CH3)CH2CH2O-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-(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] As monomer (b), X 2 It is preferable that the monomer (b) is a hydrogen atom and is an acrylate or acrylamide. Monomer (b) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

[0209] (c) Monomers containing ionic groups The vinyl polymers of this disclosure may include repeating units derived from an ionic group-containing monomer (c). 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, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0211] Monomers having anionic groups include monomers having a carboxyl group, a sulfonic acid group, or a phosphate group. Specific examples of monomers having anionic groups include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylate phosphoric acid, vinylbenzenesulfonic acid, acrylamide tert-butylsulfonic acid, or salts thereof.

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

[0213] In monomers having a cationic group, examples of cationic groups are amino groups, preferably tertiary and quaternary amino groups. In tertiary amino groups, the two groups bonded to the nitrogen atom are preferably the same or different aliphatic group having 1 to 5 carbon atoms (especially alkyl groups), aromatic groups having 6 to 20 carbon atoms (aryl groups), or aromatic aliphatic groups having 7 to 25 carbon atoms (especially aralkyl groups, e.g., benzyl group (C6H5-CH2-)). In quaternary amino groups, the three groups bonded to the nitrogen atom are preferably the same or different aliphatic group having 1 to 5 carbon atoms (especially alkyl groups), aromatic groups having 6 to 20 carbon atoms (aryl groups), or aromatic aliphatic groups having 7 to 25 carbon atoms (especially aralkyl groups, e.g., benzyl group (C6H5-CH2-)). In tertiary and quaternary amino groups, the remaining group bonded to the nitrogen atom may have an ethylenically unsaturated double bond. The cationic group may also be in salt form.

[0214] The cationic group, which is a salt, is a salt with an acid (organic or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid), are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and their salts are preferred.

[0215] Specific examples of monomers having cationic groups 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., acetates) 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., acetates) 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 - SO3 Black3 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 monomers The vinyl polymers of this disclosure may have repeating units derived from a halogenated olefin monomer (d). The halogenated olefin monomer (d) does not have to contain fluorine atoms. Preferably, the halogenated olefin monomer (d) is an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms, or iodine atoms. Preferably, the halogenated olefin monomer (d) is a chlorinated olefin having 2 to 20 carbon atoms, and more preferably an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred specific examples of halogenated olefin monomer (d) are halogenated vinyl, for example, vinyl chloride, vinyl bromide, vinyl iodide, and halogenated vinylidene, for example, vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred because it provides high water repellency (especially water repellency durability). The presence of repeating units derived from the halogenated olefin monomer (d) can improve the wash durability provided by the vinyl polymer.

[0218] (e) Crosslinkable monomers The vinyl polymers of this disclosure may include repeating units 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 reactive groups include hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like.

[0219] Examples of crosslinkable monomers may be vinyl monomers having a reactive group, mono(meth)acrylates, di(meth)acrylates, or di(meth)acrylamides 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 monomers The vinyl polymers of this disclosure may have repeating units 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 polymers of this disclosure may also be styrene polymers having repeating units 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, for example, it may have 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 monocyclic, polycyclic, or bridged ring group, with bridged ring group being preferred. The cyclic hydrocarbon group may have a chain-like group (for example, a halogen atom, a linear or branched hydrocarbon group (particularly a linear or branched hydrocarbon group having 1 to 20 carbon atoms)).

[0224] The number of carbon atoms in the cyclic hydrocarbon group may be 4 or more, 6 or more, or 8 or more, and may be 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less.

[0225] Specific examples of cyclic hydrocarbon groups include cyclohexyl group, t-butylcyclohexyl group, adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, bornyl group, isobornyl group, norbornyl group, dicyclopentanyl group, dicyclopentenyl group, benzyl group, phenyl group, naphthyl group, 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (e.g., cyclohexylene group, adamantylene group, phenylene group, naphthylene group, etc.), and substituted groups thereof.

[0226] Specific examples of cyclic hydrocarbon group-containing monomers (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 obtained by substituting these acrylates with acrylamide. These may be used alone or in combination of two or more.

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

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

[0229] [Composition of polymer] The vinyl polymer of this disclosure may be one polymer selected from the group consisting of monomers (a) to (g), or it may be a copolymer of two or more monomers. The combinations of monomers (a) to (g) that constitute the repeating units of the vinyl polymer of this disclosure are not particularly limited, but for example, they are as follows (parentheses omitted). a a+ 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 monomer (a) or in addition to monomer (a). Other monomers (g) may also be used in combination with the above combinations. 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, relative to the vinyl polymer, and may also 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.

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

[0232] Of the monomer (a), the amount of 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 also 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] Of monomer (a), the amount of monomer (a2) 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 also 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 also 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. The amount of 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, or 1000 parts by weight or more, and may also be 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 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, relative to the vinyl polymer, and may also 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. The amount of 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, or 1000 parts by weight or more, and may also be 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 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, relative to the vinyl polymer. Alternatively, 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, relative to the vinyl polymer. The amount of 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, or 1000 parts by weight or more, relative to 100 parts by weight of repeating units derived from monomer (a). Alternatively, it may be 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.

[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, relative to the vinyl polymer, and may also 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. The amount of 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, or 1000 parts by weight or more, and may also be 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 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 also 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. The amount of 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, or 1000 parts by weight or more, and may also be 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 repeating units derived from monomer (a).

[0239] The amount of repeating units derived from the 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 also 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. The amount of repeating units derived from the 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, or 1000 parts by weight or more, and may also be 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 repeating units derived from the monomer (a).

[0240] The amount of repeating units derived from the 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 also 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. The amount of 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, or 1000 parts by weight or more, and may also be 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 repeating units derived from monomer (a).

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

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

[0243] In solution polymerization, monomers are dissolved in an organic solvent in the presence of a polymerization initiator, followed by nitrogen purging and heating and stirring at a temperature 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 monomer.

[0244] Organic solvents are inert to monomers and dissolve them, and may include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone, and methyl isobutyl ketone), and alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically ethanol, butanol, and 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 3000 parts by weight, for example, 50 to 2000 parts by weight, per 100 parts by weight of the total monomers.

[0245] In emulsion polymerization, a method is employed in which monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and then polymerized by stirring at a temperature of 50-80°C for 1-20 hours after nitrogen purging. Polymerization initiators include water-soluble ones 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 ones 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 of 0.01-10 parts by weight per 100 parts by weight of monomer.

[0246] To obtain a polymer aqueous dispersion with excellent stability during storage, it is desirable to polymerize the monomers by micronizing them in water using an emulsifying device that can impart strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer. Various emulsifiers, including anionic, cationic, and nonionic types, can be used as emulsifiers, typically in an amount ranging from 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 miscible, it is preferable to add a compatibilizer that allows them to be sufficiently miscible, such as a water-soluble organic solvent or a low molecular weight monomer. Adding a compatibilizer can improve emulsifying and copolymerizing properties.

[0247] As the water-soluble organic solvent, the organic solvents mentioned above may be used. For example, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc., may be used in a range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. In addition, as low molecular weight monomers, methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., may be used in a range 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] In polymerization, a chain transfer agent may be used. 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 (especially alkyl mercaptans (e.g., with 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. 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 monomer.

[0249] [Isocyanate derivatives] The water-repellent compositions of this disclosure may contain isocyanate derivatives, and preferably may contain isocyanate derivatives obtained by the reaction of an active hydrogen compound and a raw material isocyanate as described below.

[0250] Isocyanate derivatives are compounds obtained by the reaction of an active hydrogen compound with a starting isocyanate, and have a portion derived from the active hydrogen-containing compound and a portion derived from the starting isocyanate. Unlike isocyanate-based curing agents, isocyanate derivatives do not usually have an isocyanate group.

[0251] Isocyanate derivatives have an -NHCO- group formed by the reaction of an active hydrogen compound with a starting isocyanate (where -NHCO- may be part of a urethane group or a urea group). The -NHCO- group is formed by the reaction of an active hydrogen-containing group (typically a hydroxyl group) of compound (a) with an active hydrogen-reactive group (typically an isocyanate group) of compound (b). Isocyanate derivatives are typically urethanes (especially polyurethanes).

[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 an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group), is preferred. The hydrocarbon group may be branched, cyclic, or linear, and 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, and 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 linear, and particularly linear. The alkyl group of the isocyanate derivative may have 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 of the isocyanate derivative may have 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 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more. The weight-average molecular weight of the isocyanate derivative may be 1,000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, or 5000 or less.

[0255] The water contact angle of the isocyanate derivative may be 50° or higher, 55° or higher, 65° or higher, 75° or higher, 85° or higher, 90° or higher, 100° or higher, or 105° or higher, 110° or higher, or 115° or higher. The water contact angle of the isocyanate derivative may be 160° or lower, 140° or lower, 130° or lower, 120° or lower, 110° or lower, 100° or lower, or 90° or lower. By having a water contact angle of the isocyanate derivative above the lower limit, good water repellency can be imparted to the substrate. The water contact angle is the static contact angle of the isocyanate derivative with respect to the 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.

[0256] [Active hydrogen compounds] Active hydrogen compounds contain active hydrogen groups that react with isocyanate groups.

[0257] Examples of active hydrogen groups include hydroxyl groups, amino groups, and carboxyl groups, but typically it is the hydroxyl 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 hydrocarbon alcohol (α1) may be a hydrocarbon group having 6 to 40 carbon atoms as described above, and the above explanation shall apply. The hydrocarbon group in hydrocarbon alcohol (α1) may preferably be an alkyl group having 12 to 30 carbon atoms as described above, and the above explanation shall apply.

[0260] Furthermore, the hydrocarbon alcohol (α1) preferably has one hydroxyl group per molecule.

[0261] Examples of hydrocarbon alcohols (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 isomiristyl alcohol, isocetyl alcohol, isostearyl alcohol, and isoicosyl alcohol; linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, icocenyl alcohol, dococenyl alcohol, tetracocenyl alcohol, hexacocenyl alcohol, and octacocenyl 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. 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 also, for example, 90 parts by weight or less, preferably 80 parts by weight or less, based on 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 also, for example, 60 parts by weight or less, preferably 45 parts by weight or less, and more preferably 30 parts by weight or less, based on 100 parts by weight of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. If the proportion of linear saturated hydrocarbon group-containing alcohol is above the lower limit mentioned above, the crystallinity of the hydrocarbon group will improve, and as a result, the water repellency of the water-repellent treated product can be improved.

[0263] [(α2) sugar alcohol / hydroxy acid modified compound] The active hydrogen compound may be a sugar alcohol / hydroxy acid modified product (α2), which is a sugar alcohol / hydroxy acid (sugar alcohol and / or hydroxy acid) modified with a hydrocarbon group having 6 to 40 carbon atoms. 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, while examples of hydroxy acids include hydroxypolycarboxylic acids. The sugar alcohol / hydroxy acid may be a substance that exists in living organisms. Examples of sugar alcohols / hydroxy acids include compounds derived from aldoses and ketoses, such as tetrose, pentose, hexose, and heptose, but are not limited to these. Specific examples include glucose, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, glycerol, galactose, talose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol, threitol, glucopyranose, and mannopyranose. Examples include sugar alcohols, taropyranose, allopyranose, altropyranose, idopyranose, globyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fusitol, iditol, inositol, pentaerythritol, dipentaerythritol, boremitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, citric acid, gluconate lactone, glyceric acid lactone, xylonate lactone, glucosamine, galactosamine, or mixtures thereof. The number of carbon atoms in the sugar alcohol / hydroxy acid may be 2 or more, 4 or more, or 6 or more, and may be 30 or less, 20 or less, or 10 or less. The average OH value of the compound (α2) may be in the range of greater than 0 to about 230, preferably about 10 to about 175, most preferably about 25 to about 140.

[0264] The sugar alcohol / hydroxy acid modified product (α2) may have 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more hydrocarbon groups having 6 to 40 carbon atoms. The sugar alcohol / hydroxy acid modified product (α2) may have 12 or fewer, 9 or fewer, 6 or fewer, or 3 or fewer hydrocarbon groups having 6 to 40 carbon atoms. The hydrocarbon groups in the sugar alcohol / hydroxy acid modified product (α2) may be the hydrocarbon groups having 6 to 40 carbon atoms as described above, and the above explanation applies. The sugar alcohol / hydroxy acid modified product (α2) may also have an alkyl group having 12 to 30 carbon atoms. The above explanation applies to alkyl groups having 12 to 30 carbon atoms.

[0265] In the sugar alcohol / hydroxy acid modified product (α2), at least one active hydrogen (e.g., hydrogen in the OH group, carboxyl group) of the sugar alcohol and / or 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 R may be substituted with an active hydrogen substituent selected from a mixture thereof. α2 is a hydrogen atom or a hydrocarbon group having 6 to 40 carbon atoms, where 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, for example, in a sugar alcohol / hydroxy acid modified product, at least one (1 or more) of the active hydrogens of the sugar alcohol / hydroxy acid may be unmodified, and this active hydrogen (e.g., an -OH group) may react with the active hydrogen reactant group (especially an isocyanate group) of compound (b) to form -NHCO-. The 6 to 40 carbon atoms in the sugar alcohol / hydroxy acid modified product (α2) are preferably alkyl groups having 12 to 30 carbon atoms as described above, and the above explanation applies.

[0266] ((α21) sorbitan modified compound) The sugar alcohol / hydroxy acid modified product (α2) may be a sorbitan modified product (α21) obtained by modifying sorbitan with a hydrocarbon group having 6 to 40 carbon atoms, and may particularly be an alkylsorbitan, with sorbitan being -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 compounds substituted with a mixture thereof (where R α2 (A hydrocarbon group has 6 to 40 carbon atoms). For example, sorbitan is -C(O)R α2 The compound may be monosubstituted, disubstituted, or trisubstituted. Here, sorbitan may contain amounts of sorbitol, isosorbide, or other intermediates or by-products. The hydrocarbon group in the sorbitan modified product (α21) may be a hydrocarbon group having 6 to 40 carbon atoms as described above, and the above explanation shall apply. The sorbitan modified product (α21) may have an alkyl group having 12 to 30 carbon atoms. The above explanation shall apply to alkyl groups having 12 to 30 carbon atoms. Commercially available sorbitan such as SPAN can be used as the alkylsorbitan.

[0267] In one embodiment, at least one active hydrogen substituent is -C(O)R α2 It is fine if R α2 The C1 is a linear or branched alkyl group having 6 to 40 carbon atoms, more preferably 7 to 21, and most preferably 11 to 21 carbon atoms. Preferred compounds include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and monosubstituted, disubstituted, and trisubstituted sorbitans derived from mixtures thereof. Particularly preferred compounds include monosubstituted, disubstituted, and trisubstituted sorbitan stearates, or sorbitan behenin.

[0268] In one embodiment, R α2 It may contain at least one unsaturated bond. An example of such a compound (at least one active hydrogen substituent is -C(O)R α2 Selected from, R α2 As an example of a compound containing at least one unsaturated bond, sorbitan trioleate (i.e., in the formula, R α2 -C7H 14 CH=CHC8H 17 Examples include, but are not limited to, palmitoleic acid, linoleic acid, arachidonic acid, and erucic acid, which are monosubstituted, disubstituted, and trisubstituted sorbitans.

[0269] In one embodiment, the sorbitan modified product (α21) has at least one active hydrogen substituent, and the active hydrogen substituent is independently -(CH2CH2O) n (CH(CH3)CH2O) m R α2 or -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 (where m is independently between 0 and 20, and n is independently between 0 and 20, and m+n is greater than 0). Such compounds are known as polysorbates and are marketed under the trademark name TWEEN. These sorbitans are R α2 Therefore, monosubstituted, disubstituted, or trisubstituted compounds can be used. Commercially available polysorbates have each R 2 From various polysorbates where H is unsubstituted, each R α2 It is known to contain a wide range of mixtures, from polysorbates in which the linear or branched alkyl group has 6 to 40 carbon atoms (fully substituted), to mixtures of various substitutions thereof. Examples of such sorbitan modified products (α21) include polysorbates such as polysorbate tristearate and polysorbate monostearate. m+n is greater than 0, and R α2Examples of sorbitan modifications (α21) containing at least one unsaturated bond include, but are not limited to, polysorbate trioleates (where R α2 C7H 14 CH=CHC8H 17 Examples include (which are commercially available under the name polysorbate 80). The sorbitan modified product (α21) may contain a mixture of compounds having various active hydrogen substituents, and R α2 A compound containing at least one unsaturated bond, and R α2 It may also contain a mixture with a completely saturated compound.

[0270] ((α22) citrate modified compound) The sugar alcohol / hydroxy acid modified product (α2) may be a citrate modified product (α22) obtained by modifying citrate with a hydrocarbon group having 6 to 40 carbon atoms, and may particularly be an alkyl citrate. For example, the citrate modified product (α22) may exist as a monosubstituted, disubstituted, or trisubstituted product having an alkyl group. The hydrocarbon group in the citrate modified product (α22) may be a hydrocarbon group having 6 to 40 carbon atoms as described above, and the above explanation shall apply. The citrate modified product (α22) may have an alkyl group having 12 to 30 carbon atoms. The above explanation shall apply to alkyl groups having 12 to 30 carbon atoms. A mixture of citrates having active hydrogen substituents of various values ​​may be used, and R α2 A compound having a hydrocarbon group having at least one unsaturated bond, and R α2 It may also contain a mixture with a compound that is a completely saturated hydrocarbon. The citrate-modified compound (α22) is -(CH2CH2O) n (CH(CH3)CH2O) m R α2 Alternatively, -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 It may have an active hydrogen substituent selected from (where R α2 (This refers to a hydrocarbon group having 6 to 40 carbon atoms). Examples of citrate-modified (α22) compounds include, but are not limited to, trialkyl citrates.

[0271] ((α23) Pentaerythritol modified compound) The sugar alcohol / hydroxy acid modified product (α21) may be a pentaerythritol modified product (α23) obtained by modifying pentaerythritol with a hydrocarbon group having 6 to 40 carbon atoms, and may be a monosubstituted, disubstituted, or trisubstituted product having a hydrocarbon group (especially an alkyl group) having 6 to 40 carbon atoms, for example, a dipentaerythriol ester. The active hydrogen substituent is -CH2C[CH2OR α2 ]3 may be included (where R α2 ( is a hydrocarbon group with 6 to 40 carbon atoms). Also, pentaerythritol modified compounds (α23) are compounds having a mixture of hydrocarbon groups with different chain lengths, or R α2 A compound containing at least one unsaturated bond, and R α2 It may contain a mixture with a completely saturated compound. The hydrocarbon group in the pentaerythritol modified product (α23) may be a hydrocarbon group having 6 to 40 carbon atoms as described above, and the above explanation shall apply. The pentaerythritol modified product (α23) may have an alkyl group having 12 to 30 carbon atoms. The above explanation shall apply to alkyl groups having 12 to 30 carbon atoms.

[0272] [(α3) Cationic active hydrogen compounds] The active hydrogen compound may be a cationic active hydrogen compound (α3) having an active hydrogen group and a cationic group.

[0273] Furthermore, the cationic active hydrogen compound (α3) preferably has two or more hydroxyl groups per molecule.

[0274] Examples of cationic groups include tertiary amino groups.

[0275] In other words, 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 to liquid media (e.g., water), and can also introduce cationic groups that have affinity for textile products (described later) into the resin, thereby improving wash durability.

[0277] More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as active hydrogen groups and a tertiary amino group as a 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, as well as trialkanolamines such as N-triethanolamine and N-triisopropanolamine, with N-methyldiethanolamine being preferred.

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

[0280] Examples of acid compounds include organic acids and inorganic acids. Examples of organic acids include acetic acid, lactic acid, tartaric acid, and malic acid, with acetic acid and lactic acid being preferred, and acetic acid being more preferred. Examples of inorganic acids include hydrochloric acid, sulfuric acid, and phosphoric acid, with hydrochloric acid being preferred. Examples of acid compounds include organic acids. If the acid compound contains an organic acid, the water repellency of the water-repellent treated product can be improved by the volatilization of the acid by heat treatment. Furthermore, the volatilization of the acid by heat treatment can improve the wash durability of the textile product from the viewpoint that the cationic group can be more easily adsorbed onto the textile product. [(α4) Other active hydrogen-containing compounds] The active hydrogen compound (α) may also contain other active hydrogen compounds (α4).

[0281] ((α41) compound) The active hydrogen compound (α4) is, R α41 -X α41 [In the formula, R α41 teeth, C1-C may contain at least one unsaturated group. 30 Linear or branched alkyl, hydroxy-functional C1-C 30 Linear or branched alkyl, hydroxy-functional linear or branched C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy-functional linear or branched organosiloxanes, thiol-functional C1-C 30 Linear or branched alkyl, amine-functionalized C1-C 30 Linear or branched alkyl, Y - R α411 R α412 R α413 N + -R α414 -(Here, Y is a halide ion, for example, Cl - It is. ), HOS(=O)2-R α414 -, or R α411 R α412 C = N - (where R α411 , R α412 , R α413 Each of them is independently -H and C1-C6 alkyl, and R α414 It is a divalent alkyl group having 1 to 20 carbon atoms. X α41 is -OH, -C(O)OH, -SH, -NH(R'), -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CH2CH2O) s (CH(CH3)CH2O) t -H is an isocyanate-reactive functional group (where R ’ is a -H or monovalent organic group, s is an integer between 0 and 50, t is an integer between 0 and 50, and s+t is greater than 0. The compound may be represented by (α41).

[0282] Compound (α41) may be a hydrophilic, water-soluble material containing at least one hydroxy-terminated polyether, where X α41 is -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CH2CH2O)s(CH(CH3)CH2O) t -H. -(CH2CH2O)- represents an oxyethylene group (EO), and -(CH(CH3)CH2O)- represents an oxypropylene group (PO). These polyethers may contain only EO groups, only PO groups, or mixtures thereof. These polyethers may also exist as the specified PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol) triblock copolymer.

[0283] In one embodiment, X α41 -OH, -C(O)OH, -SH, -NH(R ’ ) and R α41 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Linear or branched alkyl, hydroxy-functional C1-C 30 Linear or branched alkyl, hydroxy-functional linear or branched C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy or amine-functional linear or branched organosiloxanes, thiol-functional C1-C 30 Linear or branched alkyl, amine-functionalized C1-C 30 Selected from linear or branched alkyl groups.

[0284] X α41 (R) may be an -OH group, and examples of such compounds (α41) include alkyl alcohols such as propanol and butanol, or aliphatic alcohols including stearyl alcohol. α41 It optionally contains at least one unsaturated group, C1-C 30Alkyl diols or polyols (R) such as linear or branched alkyls, ethanediol, propanediol, butanediol, or hexanediol. α41 These are hydroxy-functional C1-C 30 Alkylene glycol ethers such as linear or branched alkyl triethylene glycol, tetraethylene glycol, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), or glycol ethers having a mixture of PEG, PPG, or THF units (R α41 These are hydroxy-functional linear or branched C1-C chains. 30 Polyether, polyester polyol (R α41 (These are hydroxy-functional linear or branched polyesters), silicone prepolymer polyols (R α41 (These are hydroxy-functional linear or branched organosiloxanes), N,N-dimethylaminoethanol (R α41 This is amine functional C1~C 30 (Straight-chain or branched-chain alkyl), choline chloride or betaine HCl (R α41 Y - R α411 R α412 R α413 N + -R α414 -is), butanone oxime (R α41 R α411 R α412 Examples include, but are not limited to, polyether polyols (where C=N-). Polyether polyols may contain only EO groups, only PO groups, only THF groups, or mixtures thereof. These polyethers may also exist as block copolymers, such as those specified by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). Polyether glycols preferably have an average molecular weight of about 200 or more, most preferably 350 to 2000.

[0285] X α41This may be -C(O)OH, and examples of such compounds (α41) include fatty acids 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 (R α41 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Hydroxy-containing acids (R) such as linear or branched alkyl, 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 These are hydroxy-functional C1-C 30 (R) mercaptoalkanoic acids (R) such as mercaptopropionic acid (which are linear or branched alkyl groups) α41 This is thiol functionality C1~C 30 Examples include, but are not limited to, linear or branched alkyl groups.

[0286] X α41 This may be -SH, and examples of such compounds (α41) include alkylthiols such as lauryl mercaptan or dodecyl mercaptan (R α41 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Examples include, but are not limited to, linear or branched alkyl groups.

[0287] X α41 This may be -NH(R'), and examples of such compounds (α41) include alkylamines such as diisopropylamine, propylamine, hexylamine, or laurylamine (R α41 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Alkanolamines (R) such as linear or branched alkyl groups, ethanolamine, or propanolamine. α41These are hydroxy-functional C1-C 30 (Linear or branched alkyl), silicone prepolymer polyamine (R α41 (These are amine-functional linear or branched organosiloxanes), alkyldiamines (R α41 This is amine functional C1~C 30 (R) are linear or branched alkyl groups, and aminoalkanesulfonic acids such as 2-aminoethanesulfonic acid. α41 HO-S(O)2R α414 - is one example, but is not limited to these.

[0288] ((α42) compound) Compound (α42) is, 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 -H is -H, and independently of each other, -H and -R α424 , -C(O)R α424 And R α424 This is a linear or branched alkyl group having 5 to 29 carbon atoms, which may independently 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 / capate), decaglyceryl di(caprylate / capate), decaglycerol, polyglycerol-3, and C18 diglycerides.

[0290] ((α43) chain extender) Compound (α4) may also be a chain extender (α43). The chain extender (α43) is a compound having two or more (for example, two) functional groups containing active hydrogen within its molecule. Known chain extenders can be used as chain extenders, and examples include aliphatic or aromatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripylene glycol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanedimethanol; aliphatic or aromatic diamines or polyamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, and diethyltoluenediamine; phenol 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, sugar alcohol modifiers, and hydroxy acid modifiers.

[0292] [Raw material: isocyanate] Isocyanate derivatives have a portion derived from the starting isocyanate.

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

[0294] Aromatic polyisocyanates are compounds having aromatic rings and isocyanate groups. The aromatic rings in an aromatic polyisocyanate may be one or more, two or more, or three or more, and may be five or fewer, four or fewer, or three or fewer.

[0295] Acyclic aliphatic polyisocyanates are aliphatic polyisocyanates that do not have a cyclic structure. Acyclic aliphatic polyisocyanates may have aliphatic hydrocarbon groups having 2 to 20 carbon atoms. The aliphatic hydrocarbon groups having 2 to 20 carbon atoms may be divalent aliphatic hydrocarbon groups. 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 embodiment, the acyclic aliphatic polyisocyanate may be a polyisocyanate compound having an isocyanate group at the terminus of an alkylene group.

[0296] Cyclic alicyclic polyisocyanates are aliphatic polyisocyanates having a cyclic structure. Cyclic alicyclic polyisocyanates have a carbon ring that is not an aromatic ring. Cyclic alicyclic polyisocyanates may have an aliphatic hydrocarbon group having 2 to 20 carbon atoms. The aliphatic hydrocarbon group having 2 to 20 carbon atoms is described in the same way as described for acyclic aliphatic polyisocyanates above.

[0297] Bridged alicyclic polyisocyanates are polycyclic compounds having a crosslinking structure in their ring structure, such as a methylene group. Bridged alicyclic polyisocyanates may also have aliphatic hydrocarbon groups having 2 to 20 carbon atoms. The aliphatic hydrocarbon groups having 2 to 20 carbon atoms are described in the same way as described for acyclic aliphatic polyisocyanates.

[0298] The raw material isocyanate may be a derivative of the raw material isocyanate. Here, examples of derivatives include isocyanurate derivatives, allophanate derivatives, polyol derivatives, biuret derivatives, urea derivatives, oxadiazinetrione derivatives, carbodiimide derivatives, uretodione derivatives, uretonimine derivatives, and the like.

[0299] The raw material 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 embodiment, the raw material isocyanate may be an isocyanurate derivative or a biuret derivative.

[0301] In one embodiment, the raw material isocyanate may be an acyclic aliphatic polyisocyanate.

[0302] Examples of raw material isocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or mixture thereof) (TDI), phenylene diisocyanate (m-,p-phenylene diisocyanate or mixture thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixture thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or Aromatic polyisocyanates selected from 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatephenyl)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 methyl caprate, 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-Isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (Isophorone diisocyanate, IPDI), Methylenebis(Cyclohexyl isocyanate (4,4'-, 2,4'- or 2,2'-Methylenebis(Cyclohexyl isocyanate or mixtures thereof) (Hydrogenated MDI), Methylcyclohex Cyclic alicyclic polyisocyanates selected from diisocyanates (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanate methyl)cyclohexane (1,3- or 1,4-bis(isocyanate methyl)cyclohexane or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrated TMXDI); Bridged cyclic alicyclic polyisocyanates selected from norbornene diisocyanate, norbornene diisocyanate methyl, bicycloheptane triisocyanate, diisocyanate methyl bicycloheptane, and di(diisocyanate methyl)tricyclodecane; [ka] [ka] Compounds selected from; and the above isocyanate, Biuret mutated body, Polyisocyanate polymers (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), Allophanate derivatives (for example, allophanate derivatives produced by the reaction of the above-mentioned polyisocyanate with a monohydric alcohol or a dihydric alcohol), Polyol derivatives (for example, polyol derivatives produced by the reaction of the above-mentioned polyisocyanate with a trihydric alcohol (for example, trimethylolpropane, etc.) (alcohol adducts, preferably trimethylolpropane adducts), Biuret derivatives (for example, biuret derivatives produced by the reaction of the above-mentioned polyisocyanate with water or amines), Urea derivatives (for example, urea derivatives produced by the reaction of the polyisocyanate and diamine mentioned above), Oxadiazinetrione derivatives (for example, oxadiazinetrione produced by the reaction of the polyisocyanate and carbon dioxide mentioned above), Carbodiimide derivatives (such as carbodiimide derivatives produced by the decarboxylation condensation reaction of the polyisocyanates mentioned above), Uretidione derivatives, Examples include 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 also, for example, 3.8 or less. The raw material isocyanate may be a polyisocyanate having multiple isocyanate groups.

[0304] [Method for synthesizing isocyanate derivatives]

[0305] To obtain an isocyanate derivative, the active hydrogen compound and the starting isocyanate are reacted. The reaction may be carried out in one step or in multiple steps in a sequential manner. For example, if the product contains unreacted active hydrogen groups or active hydrogen reactive groups, the synthesis may be carried out sequentially. Sequential reactions are particularly useful when using substituted sugar alcohols with a high number of OH groups. The 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 the starting isocyanate may be blended such that the equivalent ratio of active hydrogen reactive groups (isocyanate groups) to active hydrogen groups (active hydrogen reactive group / active hydrogen group) is, for example, 1.2 or more, preferably 1.5 or more, and for example, 2.0 or less.

[0306] [Composition of isocyanate derivatives] The amount of the moiety derived from compound (α) may be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight, relative to 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, relative to 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 portion derived from the sugar alcohol / hydroxy acid modified product (α2) may be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight relative to the portion derived from the active hydrogen compound. The amount of the portion derived from the sugar alcohol / hydroxy acid modified product 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.

[0309] The amount of the portion derived from the cationic active hydrogen compound (α3) may be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight relative to 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, relative to 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% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight 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% 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.

[0311] The amount of the portion derived from the raw material isocyanate may be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight, relative to the isocyanate derivative. The amount of the portion derived from the raw material 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, relative to the isocyanate derivative.

[0312] [(B) Amount of isocyanate derivative] The amount of 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 polymer (A). The amount of 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 polymer (A).

[0313] 〔wax〕 The water-repellent composition in this disclosure preferably contains a wax in addition to the vinyl polymer, particularly the hydrocarbon group-containing monomer (a). The inclusion of a wax allows for a good combination of water repellency and slip resistance. The water-repellent composition in this disclosure may contain both silicone and wax, or it may contain only one of silicone and 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 also be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of the wax above the lower limit, good liquid repellency (especially oil repellency) can be imparted to the substrate. The HD contact angle is the static contact angle of the wax with respect to the spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after dropping.

[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 also be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. By having a water contact angle of the wax above the lower limit, good liquid repellency (especially water repellency) can be imparted to the substrate. The water contact angle is the static contact angle of the wax with respect to the 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.

[0316] The wax may be low molecular weight (for example, molecular weight of 1000 or less, or 500 or less) or high molecular weight. If the wax is high molecular weight, 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, 100000 or more, 300000 or more, or 500000 or more, and may also be 10000000 or less, 7500000 or less, 5000000 or less, 3000000 or less, 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 or less, 7500 or less, 5000 or less, or 3000 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 also 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 of 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 plant waxes, and mineral waxes. Paraffin wax is preferred. Specific examples of compounds constituting the wax are normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, 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, hexatriacontane). The number of carbon atoms in the compounds constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500 or 300 to 1000. These may be used individually 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, and 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, montane wax, ozokerite wax, ceresin wax, and petrolatum wax; and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, and polypropylene wax, with paraffin wax or microcrystalline wax being preferred. The wax in this disclosure may be a hydrocarbon wax, preferably a linear aliphatic hydrocarbon, for example, a linear or branched hydrocarbon, and particularly a linear hydrocarbon.

[0321] 〔silicone〕 The water-repellent composition in this disclosure may contain silicone.

[0322] Silicone is, formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )2-O-] b -Si(R 53 )3(S1) [In the formula, R 51 Each of these 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. R 53 Each of these 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 greater than or equal to 0, b represents an integer greater than or equal to 1, and (a+b) is between 5 and 200. It may be a polymer shown in [the formula].

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

[0324] Silicones may have at least one long-chain hydrocarbon group. For example, R in formula (S1) 51 At least one of R 53 At least one of the following, or R 51 and R 53 At least one of each of them may be a long-chain hydrocarbon group, 51 At least one of the groups (for example, one) may be a long-chain hydrocarbon group. Here, the long-chain hydrocarbon group may be a saturated hydrocarbon group having 6 or more carbon atoms, 10 or more carbon atoms, 15 or more carbon atoms, 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 are hexyl group (6 carbon atoms), octyl group (8 carbon atoms), lauryl group (12 carbon atoms), myristyl group (14 carbon atoms), stearyl group (18 carbon atoms), behenyl group (22 carbon atoms), tricosyl group (23 carbon atoms), lignoceryl group (tetracosyl group, 24 carbon atoms), cellotyl group (hexacosyl group, 26 carbon atoms), montyl group (octacosyl group, 28 carbon atoms), merisyl group (triacontane group, 30 carbon atoms), and dotriacontane group (32 carbon atoms).

[0325] In terms of being easy to manufacture industrially and readily available, the long-chain hydrocarbon group R51 and R 53 Other than R 51 and R 53 It is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0326] a is a non-negative integer. In terms of ease of industrial manufacture and availability, a may be 40 or less, 30 or less, or 20 or less, and preferably 30 or less.

[0327] The sum of a and b is between 5 and 200. Preferably, the sum of a and b is between 10 and 100, and more preferably between 40 and 60, in terms of ease of industrial manufacture, availability, and handling. a may be between 0 and 150, for example, 1 and 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] If a or b is 2 or more, there are multiple R 51 and R 52 Each of these may be the same or different.

[0329] R 51 and R 53 Base (for example, when expressed by the following formula (S2) R 51 and R 52 Base and R 53 It is preferable that 50 mol% or more of the total number of groups are methyl groups.

[0330] The order of existence of the repeating units enclosed by a or b is not limited to the order shown in the chemical formula, but is arbitrary. That is, the silicone may be a random polymer or a block polymer.

[0331] For example, silicone is given by formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )(R 52 )-O-]b -Si(R 53 )3(S2) [In the formula, R 51 Each of these 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. R 52 Each of these independently represents a long-chain hydrocarbon group. R 53 Each of these 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 greater than or equal to 0, b represents an integer greater than or equal to 1, and (a+b) is between 5 and 200. It may be a polymer shown in [the formula]. In equation (S2), R 51 and R 53 It 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 as follows: [ka] [In the formula, a represents an integer between 0 and 150, b represents an integer between 1 and 150. (a+b) is between 5 and 200. n is an integer between 1 and 36 (preferably n is the number of carbon atoms in the long-chain hydrocarbon group).

[0333] Silicones can be synthesized by conventionally known methods. For example, a silicone can be obtained by hydrosilylation of an α-olefin with a silicone having an SiH group.

[0334] Examples of silicones having SiH groups include methyl hydrogen silicone with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methyl hydrogen siloxane. Among these, methyl hydrogen silicone is preferred because it is easy to manufacture industrially and readily available. Hydrogen silicone (e.g., methyl hydrogen silicone) is a type of polydiorganosiloxane in which part of the side chain is replaced with hydrogen, and the hydrogen atoms are directly bonded to silicon atoms. When using hydrogen silicone, a catalyst may be used to improve reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine-based catalysts can be used. Organic acid metal salts are preferred as catalysts, and fatty acids are preferred as organic acids. Zinc stearate can be used, for example. It is preferable to use the catalyst at a concentration of 10 to 40% relative to the methyl hydrogen silicone, as this makes it easier to exhibit its effect. Two or more types of amino-modified silicones, epoxy-modified silicones, carboxy-modified silicones, and methyl hydrogen silicones may be mixed. All of them are silicones having reactive groups and preferably have film-forming properties. Film-forming properties refer to the ability of a silicone to form a solid film, rather than an oily or gel-like film, after being applied to the fiber surface in an emulsion state.

[0335] Alpha-olefins are compounds from which long-chain hydrocarbon groups are derived in silicones. Specific examples of alpha-olefins include 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triaconthene, and 1-dotriaconthene. The hydrosilylation reaction may be carried out by reacting the α-olefin with the SiH group-containing silicone in a stepwise or one-time manner, if necessary, in the presence of a catalyst.

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

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

[0338] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted as appropriate. 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. Hydrosilylation reactions are preferably carried out under an inert gas atmosphere. Examples of inert gases include nitrogen and argon. The reaction will proceed even without a solvent, but a solvent may be used. Examples of solvents include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0339] (Reactive silicone) The silicone may include a reactive silicone. Examples of reactive silicones include polysiloxanes having reactive groups in the side chain, one end, both ends, or both ends. However, from the viewpoint of having excellent slip resistance and water repellency, a polysiloxane having reactive groups in the side chain and / or both ends may also be used. The reactive silicone is not particularly limited as long as it has reactive groups in the molecule, but examples include amino-modified silicones, epoxy-modified silicones, carboxy-modified silicones, and hydrogen-modified silicones. The reactive silicone may be one in which one or more substituents in the above formula (S1) or formula (S2) are substituted with reactive groups.

[0340] Examples of amino-modified silicones include those having a structure in which an amino group is bonded to an organic group directly attached to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Alkylene groups with 2 or more carbon atoms are preferred. Divalent aromatic groups with 6 or more carbon atoms are preferred. The amino group may be a primary, secondary, or tertiary amino group. Examples of organic groups to which an amino group is bonded include: 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 or at the terminal ends of the polysiloxane.

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

[0342] Examples of carboxylated silicones include those having a structure in which a carboxyl group is bonded to an organic group directly connected to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Alkylene groups with two or more carbon atoms are preferred. Divalent aromatic groups with six or more carbon atoms are preferred. Examples of such functional groups include 3-carboxypropyl and 2-carboxyethyl groups. These functional groups may be located on the side chains or at the terminals of the polysiloxane.

[0343] (Silicone resin) Silicone may contain silicone resin. Silicone resin is R3SiO 1 / 2 Units (M units), RSiO 3 / 2 Units (T units) and SiO 4 / 2 A silicone resin consisting of at least one selected from units (Q units), where R is a linear or branched monovalent alkyl group having 1 to 18 carbon atoms, excluding silicone resins consisting only of M units or only of Q units). Silicone resin (3) is R2SiO 2 / 2 It is preferable to omit the units (D units) from the viewpoint of achieving the effects of this invention.

[0344] The silicone resin is preferably in a sol state. Examples of R include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, cetyl group, stearyl group, etc. However, considering the stability, availability of raw materials, and cost when the silicone resin (3) is in a sol state, R is preferably a methyl group, and in particular, it is preferable that 90% or more of all R are methyl groups. Note that different types of groups may be used in combination for R.

[0345] R2SiO in silicone resin 2 / 2 The inclusion of units (D units) may impair the low slipperiness of the water-repellent composition. Furthermore, a silicone resin consisting solely of Q units may hinder the water-repellent performance of the water-repellent composition.

[0346] Examples of silicone resin structures include (i) 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. Preferably, (i) silicone resins consisting of M units and Q units and (v) silicone resins consisting only of T units. The molar ratio (M / Q) of M units to Q units in (i) silicone resins consisting of M units and Q units is preferably M / Q = 0.6 to 1.3, and more preferably M / Q = 0.8 to 1.1. Two or more of these silicone resins may be used in combination.

[0347] Furthermore, the silicone resin (3) may contain structural units that include hydroxyl groups bonded to silicon atoms. Specifically, (HO)RSiO 2 / 2 Units, (HO)2RSiO 1 / 2 Unit: (HO)SiO 3 / 2 Unit: (HO)2SiO 2 / 2 Unit: (HO)3SiO 1 / 2 The units may be listed, and some of the hydroxyl groups may be alkoxy groups represented by RO groups.

[0348] A sol containing silicone resin can be obtained by a manufacturing method described in Patent No. 3852921, which involves uniformly dispersing and polymerizing organodisiloxane, tetraalkoxysilane and their partially hydrolyzed condensates in water containing a surfactant, or by a manufacturing method which involves hydrolyzing the silane compounds shown below in water.

[0349] This paper details a method for producing silane compounds by hydrolyzing them in water. Any silane compound can be used as a raw material for production, as long as it has one, three, or four hydrolyzable groups, and contains an alkyl group that satisfies the above conditions, and the hydrolyzable group is either chlor or alkoxy.Specifically, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrichlorosilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyl Lichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrichlorosilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, 2-ethylhexyltrichlorosilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, decyltriethoxysilane, cetyltrichlorosilane, cetyltrimethoxysilane, cetyltriethoxy Silane, stearyltrichlorosilane, stearyltrimethoxysilane, stearyltriethoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, dimethylethylchlorosilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylpropylchlorosilane, dimethylpropylmethoxysilane, dimethylpropylethoxysilane, dimethylisopropylchlorosilane, dimethylisopropylmethoxysilane, dimethylisopropylethoxysilane, dimethylisopropylethoxysilane, dimethylisopropyl methoxysilane, dimethylisopropylethoxysilane, dimethyl Methylhexylchlorsilane, dimethylhexylmethoxysilane, dimethylhexylethoxysilane, dimethyldecylchlorsilane, dimethyldecylmethoxysilane, dimethyldecylethoxysilane, dimethylcetylchlorsilane, dimethylcetylmethoxysilane, dimethylcetylethoxysilane, dimethylstearylchlorsilane, dimethylstearylmethoxysilane, dimethylstearylethoxysilane, and their partial hydrolysates are examples of usable silane compounds, but the usable silane compounds are not limited to these.Due to their ease of handling, ease of removing by-products, and availability of raw materials, methoxysilane or ethoxysilane is more preferable. One or more of these silane compounds may be used.

[0350] Common methods that are normally known can be used to hydrolyze silane compounds in water. These include methods such as adding the silane compound dropwise to water while carrying out the hydrolysis reaction, or mixing the water and silane compound together and then carrying out the hydrolysis reaction. A hydrolysis catalyst may be used when carrying out the hydrolysis reaction. Conventional known catalysts can be used as hydrolysis catalysts, and it is preferable to use acidic or alkaline catalysts. In the case of acidic catalysts, solid acids such as hydrogen halides, carboxylic acids, sulfonic acids, acidic or weakly acidic inorganic salts, and ion exchange resins are preferred. In the case of alkaline catalysts, 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 can be used. It is preferable to adjust the amount of catalyst added so that the pH of the aqueous solution is 2 to 7 and 7 to 12. After the reaction is complete, a neutralizing agent to neutralize the acidic or alkaline catalyst may be added as needed.

[0351] A surfactant may be added to the aqueous solution to disperse the silane compound and the hydrolysis reaction product in water. There are no particular restrictions on the surfactant, but for example, anionic surfactants such as alkyl sulfates, alkylbenzene sulfons, and alkyl phosphates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene oxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene fatty acid esters; cationic surfactants such as quaternary ammonium salts and alkylamine acetates; and amphoteric surfactants such as alkyl betaines and alkylimidazolines can be used, either alone or in combination of two or more. Furthermore, surfactants that exhibit acidity or alkalinity can also be used as hydrolysis catalysts. There are no particular restrictions on the amount of surfactant to be added, but it is preferable to add 1 to 50 parts by weight per 100 parts by weight of the silane compound. If the amount is less than 1 part by weight, the effect of adding the surfactant will not be sufficiently obtained, and if it is more than 50 parts by weight, the water repellency of the water repellent may be impaired.

[0352] A mixture of water and a silane compound may be mixed with a hydrolysis catalyst and surfactant as needed, and the hydrolysis reaction may be carried out at 0-90°C for 10 minutes to 24 hours. Afterward, a neutralization reaction may be carried out as needed to obtain silicone resin. Alcohols and neutralization salts produced as by-products of the hydrolysis reaction can be removed by vacuum distillation or filtration. Various additives can be incorporated into this silicone resin. For example, preservatives and thickeners can 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% or more by weight, 0.03% or more by weight, 0.5% or more by weight, 1% or more by weight, 3% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, or 30% or more by weight, and may also be 60% or less by weight, 50% or less by weight, 40% or less by weight, 30% or less by weight, 20% or less by weight, 10% or less by weight, 5% or less by weight, or 3% or less by weight.

[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 polymer (A) and compound (C), and may also 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% to 95% by weight relative to the sum 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, based on 100 parts by weight of the total amount of polymer (A), dispersant (B), and compound (C), and 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, based on 100 parts by weight of the total amount of polymer (A), dispersant (B), and compound (C). 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 preferred amount of compound (C) is 0 to 80 parts by weight per 100 parts by weight of the total amount of polymer (A), dispersant (B), and compound (C).

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

[0357] [Liquid media] The water-repellent composition in this disclosure may include 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 in this disclosure is preferably an aqueous dispersion or aqueous dispersion.

[0358] Examples of organic solvents include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes with 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 compounds having at least one hydroxyl group (e.g., polyols such as alcohols and glycol-based solvents, ethers of polyols (e.g., monoethers)). These may be used individually or in combination of two or more.

[0359] The water-repellent composition in this disclosure may be an organic solvent solution or an organic solvent dispersion. An organic solvent solution means a liquid in which the solute is dissolved in the solvent and forms a homogeneous phase. An organic solvent dispersion means a liquid in which the solute is suspended or floating in the solvent as particulate matter and can be separated into solute (dispersed phase) and solvent (dispersion medium) by centrifugation or the like.

[0360] [Amount of liquid medium] The amount of 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, or 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, or 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 1 part by weight of 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, or 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 1 part by weight of polymer (A).

[0362] The amount of 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, per 1 part by weight of polymer (A), and may also 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.

[0363] [Organic acid] The water-repellent compositions of this disclosure may contain organic acids. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, and sulfinic acids, with carboxylic acids being particularly preferred. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, and citric acid, with formic acid or acetic acid being particularly preferred. In this disclosure, one organic acid may be used, or two or more may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0364] [Amount of organic acids] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more per 100 parts by weight of polymer (A), and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the water-repellent composition is 3 to 10, for example 5 to 9, particularly 6 to 8. The water-repellent composition may also be acidic (pH 7 or less, for example 6 or less).

[0365] [Inorganic acid] The water-repellent compositions of this 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 this disclosure, one inorganic acid may be used, or two or more may be used in combination. Adding 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 per 100 parts by weight of polymer (A), and may also 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 also be acidic (pH 7 or less, for example 6 or less).

[0367] [Hardening agent] The water-repellent compositions of this disclosure may contain a curing agent (an active hydrogen-reactive compound or an active hydrogen-containing compound). If the water-repellent composition is for paper (for example, an oil-resistant agent for paper), it may not contain a curing agent.

[0368] The curing agent (crosslinking agent) in the water-repellent composition can effectively 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 active hydrogen-reactive compounds are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds are 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. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). A blocked isocyanate compound is a compound in which the isocyanate groups of an isocyanate compound are masked with a blocking agent to suppress the 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, and 2,6-diiso These include 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 individually or in combination of two or more.

[0372] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or mixtures thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used individually 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-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate or mixtures thereof, 2,4- or 2,6-tolylenediisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used individually or in combination of two or more.

[0374] Examples of polyisocyanate derivatives include various derivatives of the polyisocyanate compounds described above, such as dimers, trimers, biuretes, allophanates, carbodiimides, uretodiones, uretoimines, isocyanurates, and iminooxadiazinediones. These may be used individually or in combination of two or more.

[0375] These polyisocyanates can be used individually or in combination of two or more types. 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, as the polyisocyanate compound. 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] Blocking agents sequester free isocyanate groups. Blocked polyisocyanate compounds can be easily reacted with hydroxyl groups by heating them to, for example, 100°C or higher, for example, 130°C or higher, which regenerates the isocyanate groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, and pyrazole compounds. Polyisocyanate compounds can be used alone or in combination of two or more.

[0377] Epoxy compounds are compounds that have 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 that has a chloromethyl group. Examples of chloromethyl group-containing compounds include chloromethyl polystyrene. Carboxyl group-containing compounds are compounds that have a carboxyl group. Examples of carboxyl group-containing compounds include (poly)acrylic acid and (poly)methacrylic acid.

[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 hardener] The amount of 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, or 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, per 100 parts by weight of polymer (A), and may also 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 this disclosure may further contain other components.

[0381] [Other ingredients] The water-repellent composition may contain other components besides those listed above. Examples of other components include water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, preservatives, antibacterial agents, deodorants, penetrating agents, etc. These may be used alone or in combination of two or more. In addition to the components listed above, other components may include texture adjusters, softeners, antibacterial agents, flame retardants, wrinkle inhibitors, crosslinking agents, film-forming aids, compatibilizers, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoaming agents, shrinkage inhibitors, wrinkle inhibitors, shape-retaining agents, drape-retaining agents, ironing-improving agents, polymer dispersants, scum dispersants, fluorescent whitening agents, dye fixatives, and antifoaming agents. 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 esters, phosphonates, and phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and its derivatives; and nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives. These may also be ion-conductive polymers obtained by polymerizing or copolymerizing monomers having cationic, anionic, or amphoteric ion-conductive groups. These may be used individually or in combination of two or more.

[0383] (Preservative) Preservatives can be used primarily to enhance preservative and bactericidal properties and maintain preservation during long-term storage. Examples of preservatives include isothiazolone-based organosulfur compounds, benzisothiazolone-based organosulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol. The preservative content is preferably 0.0001 to 1% by weight relative to the total weight of the water-repellent composition. If the preservative content is above the lower limit of the above range, the effect of adding the preservative is sufficiently obtained, and if it is below the upper limit, the storage stability of the water-repellent composition is good.

[0384] (Antibacterial agent) Antibacterial agents are components that suppress the growth of bacteria on fibers and also suppress the generation of unpleasant odors derived from microbial decomposition products. Examples of antibacterial agents include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0385] (Deodorizer) Examples of deodorizers include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (such as the zinc complex of trisodium methylglycinediacetate described in International Publication No. 2012 / 090580).

[0386] (Anti-slip agent) This component has the effect of suppressing slippage of fibers and shifting of seams during sewing and wearing. Examples of anti-slip agents include polysiloxane compounds, colloidal silicas, silicone resin derivatives, colloidal organosilicones, and amino-modified silicones.

[0387] (Fabric softener) Fabric softeners are ingredients that give fabrics a soft and smooth texture. Examples of fabric softener ingredients include cationic surfactants such as quaternary ammonium salts and amine salts; anionic surfactants such as soap, sulfated oils, higher alcohol sulfate salts and sulfonates; nonionic surfactants such as polyhydric alcohols and polyethylene glycols; amphoteric surfactants such as betaine and amino acid types; and siloxane resins.

[0388] [Amount of other ingredients] The individual or total amounts 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, per 100 parts by weight of polymer (A), and may also 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 a water-repellent composition> A method for producing a water-repellent composition may include a step of reacting (polymerizing) silicon-containing monomers in a medium containing silicon-containing monomers (e.g., a liquid medium) to obtain a polymer (A). A dispersant (B) may be included in the medium or may be combined with polymer (A) after polymerization. By such a method, the water-repellent composition of this disclosure can be obtained.

[0390] Polymerization methods include, for example, suspension polymerization and emulsion polymerization. From the viewpoint of obtaining an emulsion of polymer (A), emulsion polymerization is preferred. The method for obtaining polymer (A) is as described above for the polymerization method of polymer (A).

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

[0392] If the polymer (A) is in the form of a dry body (e.g., a powder), the water-repellent composition of this disclosure can be obtained by dispersing the dry polymer (A) together with a dispersant (B) in a liquid medium.

[0393] In one embodiment, the method for producing a water-repellent composition is: A step of obtaining at least one compound (C) selected from the group consisting of vinyl polymers, isocyanate derivatives, waxes, and silicones, and The process may further include a step of combining a polymer (A), a dispersant (B), and a compound (C).

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

[0395] Compound (C) obtained in the process of obtaining compound (C) may be in the form of a dry substance (e.g., a powder) or a dispersion in a liquid medium. If compound (C) is dispersed in a dispersion, such dispersion may contain a dispersant (B).

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

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

[0398] <Uses of water-repellent compositions> Examples of applications for the water-repellent compositions in this disclosure include external treatment agents (surface treatment agents) or internal treatment agents, water-repellent compositions (water repellents, oil repellents or water- and oil-repellent agents, etc., especially water repellents), antifouling agents, dirt removal agents, release agents, mold release agents (external mold release agents or internal mold release agents), and the like.

[0399] <Manufacturing method for processed products> The method for manufacturing the processed product in this disclosure includes a step of treating a substrate with a water-repellent composition.

[0400] [Processed Products] Substrates that can be treated with the water-repellent composition of this disclosure include fibrous substrates, stone materials, 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 given. For example, natural animal and plant fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or blends thereof. An example of a substrate treated with the water-repellent composition will be described in detail regarding woven and knitted fabrics.

[0401] (Woven or knitted fabrics) • Manufacturing methods for woven and knitted fabrics Woven and knitted fabrics can be obtained by weaving and knitting long and short fibers made from the above-mentioned fibers to obtain raw fabric, and then by post-processing and water-repellent treatment. Weaving and knitting can be carried out using known looms and knitting machines, and the preparation process preceding weaving and knitting can also be carried out using known equipment.

[0402] Woven or knitted fabrics can be post-processed using known scouring and dyeing methods and equipment suitable for the fiber material of the woven or knitted fabric.

[0403] After post-processing, the woven or knitted fabric may be treated to be water-repellent. For water-repellent treatment, first, an aqueous solution containing a water-repellent agent (which may be a water-repellent agent composition as described in this disclosure) is prepared. Next, the aqueous solution is applied to the woven or knitted fabric after the post-processing using a padding method, spray method, slit coater method, etc., and after drying, it is subjected to dry heat treatment. The aqueous solution may also contain a crosslinking agent, softener, antistatic agent, etc., as needed. After water-repellent treatment, the woven or knitted fabric may be calendered.

[0404] Woven and knitted fabrics are ideally suited for clothing applications where water repellency is required, particularly for sportswear such as outdoor wear, skiing, snowboarding, and golf, as well as uniform wear.

[0405] • Laminated fabric The present disclosure may also be provided as a laminated fabric having a breathable waterproof layer on one side of the woven or knitted fabric. The breathable waterproof layer may be directly laminated to the woven or knitted fabric, or it may be laminated to the woven or knitted fabric via an adhesive layer. When the laminated fabric of the present disclosure is used for clothing or the like, the woven or knitted fabric side is positioned to repel rainwater, etc.

[0406] • Breathable waterproof layer A breathable waterproof layer is a layer that covers one side of a woven or knitted fabric, and is formed from a resin or structured film that has waterproof and breathable properties.

[0407] The breathable waterproof layer may be formed by directly applying resin (the resin constituting the breathable waterproof layer) to the woven or knitted fabric, or it may be laminated to one side of the woven or knitted fabric via an adhesive layer as described later.

[0408] The resins used to make up the breathable waterproof layer are not particularly limited, but non-porous and porous resins are used. Non-porous resins include polyurethane resins and polyester elastomer resins that have hydrophilic components to provide breathability. Porous resins include polyurethane resins that form wet porous membranes and polyurethane resins that are made porous by electrospinning, as well as porous membranes made of PTFE, PE, and PP.

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

[0410] A breathable waterproof membrane having a microporous structure can be obtained by a wet solidification method using a DMF solution of polyurethane resin containing inorganic fine powder. Examples of inorganic fine powders include fine powders made from 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 inorganic fine powder content is preferably 3 to 50% by weight, and more preferably 5 to 50% by weight, relative to the total amount of the moisture-permeable waterproof layer.

[0411] The thickness of the breathable waterproof layer is preferably 5 μm or more, and more preferably 10 to 30 μm. A thickness within this range provides an excellent balance of waterproofing and breathability, and also offers advantages in terms of texture.

[0412] ·Adhesive layer The laminated fabric preferably includes an adhesive layer. In other words, it is preferable that the woven or knitted fabric and the breathable waterproof layer are laminated with an adhesive layer in between. Furthermore, it is preferable for the adhesive layer to be a discontinuous layer, such as a dot or grid pattern, from the standpoint of breathability.

[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 breathable waterproof layer. For example, if a resin mainly composed of polyurethane resin is selected as the resin that constitutes the breathable waterproof layer, it is preferable to use an adhesive layer made of polyurethane adhesive. The polyurethane adhesive may be of any structure, such as ether-based, ester-based, or polycarbonate-based.

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

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

[0416] • Lining fabric In the laminated fabric of this disclosure, a lining fabric may be laminated on the breathable waterproof layer (on the side of the breathable waterproof layer opposite to the side on which the woven or knitted fabric of this disclosure is laminated). The lining fabric can protect the breathable waterproof layer, and the waterproofness (water pressure resistance) and strength can be further improved.

[0417] Examples of lining fabrics include various woven and knitted fabrics. Among these, knitted fabrics are preferable because, compared to woven fabrics, the constituent threads tend to protrude more easily from the surface, resulting in a less flat surface. This allows for a greater anchoring effect, making it less likely to separate from the breathable waterproof layer.

[0418] Furthermore, tricot knit fabric is preferable because it allows for the production of long lengths of raw material during the knitting process, resulting in fewer seams and enabling uniform lamination on a breathable waterproof layer.

[0419] The material of the fibers constituting the lining fabric is not particularly limited and can be selected as appropriate, but nylon fibers are preferred. This is because, since acid dyes are generally used for nylon fibers, the migration and sublimation of disperse dyes to the breathable waterproof layer, which is a problem with polyester fibers and the like that use disperse dyes, is less likely to occur. The form of the constituent fibers of the lining fabric (long fibers, short fibers, or spun yarn) or the fineness is not particularly limited and can be selected as appropriate within a range that does not impair the effects of this disclosure.

[0420] • Characteristics of laminated fabric Laminated fabrics have excellent waterproofing properties. A good example of the waterproofing properties of the laminated fabrics of this disclosure is a water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method), which is, for example, 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] Laminated fabrics have excellent moisture permeability. A preferred example of the moisture permeability of the laminated fabrics of this disclosure is a moisture permeability of, for example, 10,000 g / m² as measured according to the JIS L 1099:2021 B-1 method (potassium acetate method). 224 hours or more, preferably 15,000 g / m² 2 24 hours or more, more preferably 20,000 g / m² 2 • 24 hours or more is a possible example. There are no particular restrictions on the upper limit of this moisture permeability, but for example, 40,000 g / m 2 24h or 35,000g / m² 2 One example is 24h·mm. Additionally, the moisture permeability measured according to JIS L 1099:2021 A-1 method (calcium chloride method) is, for example, 4000g / m³. 2 24 hours or more, preferably 8000 g / m² 2 24 hours or more, more preferably 10,000 g / m² 2 • 24 hours or more is mentioned. Regarding the upper limit of this moisture permeability, as a limitation of the measurement method, it is 13,000 to 15,000 g / m². 2 It will be approximately 24 hours.

[0422] In the laminated fabric of this disclosure, the peel strength between the woven or knitted fabric and the breathable waterproof layer, measured according to 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 other applications.

[0423] • Manufacturing method of laminated fabric The method for manufacturing the laminated fabric is not particularly limited, but examples include the first and second manufacturing methods shown below. First manufacturing method: Includes the step of forming the moisture-permeable waterproof layer by applying the resin constituting the moisture-permeable waterproof layer to the surface of a woven or knitted fabric. A second manufacturing method includes the steps of forming an adhesive layer on a woven or knitted fabric or a breathable waterproof layer, and bonding the woven or knitted fabric and the breathable waterproof layer via the adhesive layer.

[0424] In the first manufacturing method, a coating method can be used to apply the resin constituting the moisture-permeable waterproof layer to the surface of the woven or knitted fabric. In the coating method, a knife coater or a comma coater can be used. Furthermore, 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, a lamination method is used as a method for forming an adhesive layer on a woven or knitted fabric or a breathable waterproof layer. In the lamination method, a resin solution or a hot melt method can be used to form the adhesive layer. First, a resin composition for forming a breathable waterproof layer (for example, a resin composition containing resin and an organic solvent) is applied to the surface of a release agent (release paper, release cloth, or release film, etc.) with a clearance, and the breathable waterproof layer is formed while adjusting the thickness, and then dried and heat-treated to obtain a film. The release agent can be removed as appropriate after lamination or curing. In addition, when laminating by the hot melt method, the release agent can be peeled off and the film can be laminated on its own. Furthermore, the breathable waterproof membrane can be laminated with membranes manufactured using solvent-free extrusion methods such as the T-die method and inflation, porous membranes manufactured by electrospinning, and porous membranes made of PTFE, PE, PP, etc.

[0426] Then, an adhesive layer is formed on the woven or knitted fabric or the breathable waterproof layer. For example, if using a resin solution, a two-component curing polyurethane resin solution, adjusted to a viscosity in the range of 500 to 5000 mPa·s, may be applied to the entire surface or in a pattern. After drying, an adhesive layer is formed, and the woven or knitted fabric and the breathable waterproof layer are bonded together via the adhesive layer, and the second manufacturing method can be carried out by pressing or heat-pressing the two together.

[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 terms, it is more preferable to use one that melts in a temperature range of about 80 to 150°C. In this case, first, the hot melt resin is melted while considering the melting point of the resin and the viscosity when melted. Then, the melted resin is applied to the woven or knitted fabric or the breathable waterproof layer to form an adhesive layer, and the woven or knitted fabric and the breathable waterproof layer are bonded together and pressed to carry out the second manufacturing method. Alternatively, if texture is important, the resin can be applied to the breathable waterproof membrane in a pattern and bonded to the woven or knitted fabric.

[0428] Subsequently, a lining fabric can be laminated onto the breathable waterproof layer using a known and appropriate method.

[0429] • Uses of laminated fabrics Laminated fabrics offer excellent water repellency and breathable waterproofing, 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] [Processing method] The water-repellent composition of this disclosure can be applied to a substrate (particularly a fibrous substrate) by conventionally known methods as a treatment agent (particularly a surface treatment agent). The water-repellent composition of this disclosure may be diluted by dispersing it in an organic solvent or water as needed, and then applied to the surface of the substrate by known methods such as immersion coating, spray coating, foam coating, etc., and then dried. After drying, a fibrous product with the solid components of the water-repellent composition attached is obtained. If necessary, it may also be applied together with a suitable crosslinking agent and cured. Furthermore, the water-repellent composition of this disclosure can be used in combination with various additives such as water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle-preventing agents, drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, insecticides, and defoaming agents. Examples of various additives may be the same as those described in "other components" in the water-repellent composition described above. The concentration of the hydrocarbon-based water-repellent resin in the treatment agent that comes into contact with the substrate may be appropriately changed depending on the application, but it may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0431] [Textile products] Various examples can be given of the fibrous base material, such as cloth products and paper products.

[0432] Examples of textile products include natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester (polyethylene terephthalate is particularly preferred), polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or blends thereof. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as fabrics and carpets. However, treatment may also be applied to fibers, yarns, and intermediate textile products (e.g., slivers or rovings) before they are made into fabric.

[0433] Examples of paper products include paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as crushed wood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine, recycled corrugated cardboard or deinked paper, paper containers, and molded products made from paper. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-grade paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive 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., cloth) by any known method 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 to or sprayed onto the textile substrate. The treated textile product textile substrate is preferably dried and cured by heating to exhibit water-repellent and oil-repellent properties. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. Good performance can also be obtained with low-temperature heating (e.g., 100°C to 140°C) in this disclosure. The heating time may be 5 seconds to 60 minutes in this disclosure, for example, 30 seconds to 3 minutes.

[0435] Alternatively, the polymer may be applied to the fibrous substrate by a cleaning method, for example, by washing or dry cleaning.

[0436] The fibrous substrate to be treated may be a cloth, which includes woven fabrics, knitted fabrics and nonwoven fabrics, cloth in the form of clothing and carpets, etc., but may also be a fiber or yarn or intermediate fibrous product (e.g., sliver or roving yarn, etc.). The water-repellent compositions of this disclosure are particularly effective in making fibrous products (e.g., synthetic fibers) water-repellent.

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

[0438] Examples of natural fibers include cellulose fibers such as cotton, flax, and pulp, as well as chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as groundwood pulp (GP), pressured groundwood pulp (PGW), and thermomechanical pulp (TMP); chemical pulps such as high-yield unbleached softwood kraft pulp (HNKP; N material), bleached softwood kraft pulp (NBKP; N material, NB material), unbleached hardwood kraft pulp (LUKP; L material), and bleached hardwood kraft pulp (LBKP, L material); recycled paper pulp 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 copolymerized 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; and polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupro, polynosic rayon, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0440] Alternatively, the fibrous base material may be leather. The manufactured polymer may be applied to the leather in the form of an aqueous solution or aqueous emulsion at various stages of leather processing, for example, during the wetting process or during the finishing process, in order to make the leather hydrophobic and oleophobic. Alternatively, the fibrous substrate may be paper. The manufactured polymer may be applied to pre-formed paper, or it may be applied at various stages of papermaking, for example, during the drying period of the paper.

[0441] "Treatment" means applying the water-repellent composition to a substrate by immersion, spraying, coating, etc. Through treatment, the polymer (A), which is the active ingredient of the water-repellent composition, penetrates into the interior of the substrate and / or adheres to the surface of the substrate. In other words, through treatment, a substrate (e.g., a textile product) to which the polymer (A) of the water-repellent composition of this disclosure is attached is obtained.

[0442] [Pretreatment of textile substrates] The fibrous substrate may be pre-treated before being treated with the water-repellent composition of this disclosure. Pre-treating the fibrous substrate can impart excellent fastness to the fibrous substrate after treatment with the water-repellent composition.

[0443] Examples of pretreatments for fiber substrates include cationization by reaction with reactive quaternary ammonium salts, anionization by sulfonation, carboxylation, phosphorylation, etc., acetylation, benzoylation, carboxymethylation, grafting, tannic acid treatment, and polymer coating after anionization.

[0444] The method for pre-treating the fiber substrate is not limited, but it can be pre-treated by conventionally known methods. The pre-treatment solution may be diluted by dispersing it in an organic solvent or water as needed, and then applied to the surface of the fiber substrate by known methods such as immersion coating, spray coating, or foam coating, followed by drying. The pH and temperature of the pre-treatment solution may be adjusted according to the desired degree of treatment. As an example of a method for pre-treating a fiber substrate, a method of pre-treating the fiber substrate with a hydrocarbon-based water repellent will be described in detail.

[0445] The pretreatment method for the fiber substrate involves applying -SO3M to the fibers. 1 (In the formula, M 1 (represents a monovalent cation) a monovalent group represented by -COOM 2 (In the formula, M 2 A monovalent group represented by (where is a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2The process may include a step of conferring at least one functional group (hereinafter sometimes referred to as a "specific functional group") selected from the group consisting of monovalent groups (each representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

[0446] M 1 Examples include H, K, Na, or ammonium ions which may have substituents. 2 Examples include H, K, Na, or ammonium ions which may have substituents. 1 or X 2 If it 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 above-mentioned specific functional groups (hereinafter sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following method. (i) A compound having the above-mentioned specific functional group is attached to the fiber material. The attachment of the compound may be such that a portion of the compound and a portion of the fiber are chemically bonded, as long as a sufficient amount of the above-mentioned specific functional group remains. (ii) Prepare a fiber in which the above-mentioned specific functional group is directly introduced into the material constituting the fiber.

[0448] (i) For example, a functional group-containing fiber can be obtained by a functional group introduction step in which the fiber material is treated with a pretreatment solution containing one or more compounds having the above-mentioned specific functional group.

[0449] There are no particular restrictions on the material of the fiber material, and examples 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 fiber material may take any form, such as fibers (tow, sliver, etc.), yarn, knitted fabrics (including interwoven fabrics), woven fabrics (including interwoven fabrics), nonwoven fabrics, and paper.

[0450] In this embodiment, from the viewpoint of obtaining good water repellency in the resulting textile product, it is preferable to use a fiber material containing polyamide and polyester as a base material. In particular, it is preferable to use nylon such as nylon 6 and nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.

[0451] The above -SO3M 1 As a compound having this property, phenolic polymers can be used. Examples of such phenolic polymers include those containing at least one compound represented by the following general formula.

[0452] JPEG0007846437000010.jpg4770 [where, X 2 ha-SO3M 3 (In the formula, M 3 (where n represents a monovalent cation) or a group represented by the following general formula, where n is an integer between 20 and 3000.

[0453] JPEG0007846437000011.jpg2858 [In the formula, M 4 This represents a monovalent cation.

[0454] The above M 3 Examples include H, K, Na, or ammonium ions which may have substituents.

[0455] The above M 4 Examples include H, K, Na, or ammonium ions which may have substituents.

[0456] The compound represented by the above general formula may, for example, be a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0457] The above-COOM 2 Examples of compounds having this property include polycarboxylic acid polymers.

[0458] As polycarboxylic acid polymers, for example, polymers synthesized by conventionally known radical polymerization methods using acrylic acid, methacrylic acid, maleic acid, etc. as monomers, or commercially available polymers can be used.

[0459] One method for producing polycarboxylic acid polymers is to add a radical polymerization initiator to an aqueous solution of the monomer and / or its salt, and heat the reaction at 30 to 150°C for 2 to 5 hours. At this time, alcohols such as methanol, ethanol, isopropyl alcohol, or aqueous solvents such as acetone may be added to the aqueous solution of the monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators using combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo polymerization initiators. These radical polymerization initiators may be used alone or in combination of two or more. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.

[0460] In radical polymerization, copolymerizable monomers can be used in addition to the monomers mentioned above. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, as well as acrylamide, acrylates, and methacrylates. Acrylates and methacrylates are preferably those having a hydrocarbon group with 1 to 3 carbon atoms, which may have substituents such as hydroxyl groups. 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 individually or in combination of two or more.

[0461] The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized by alkali metals or amine compounds. Examples of alkali metals include sodium, potassium, and lithium, while examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0462] The weight-average molecular weight of the polycarboxylic acid polymer is preferably 1,000 to 20,000, and more preferably 3,000 to 15,000, from the viewpoint of obtaining good water repellency in the resulting textile product.

[0463] For polycarboxylic acid polymers, commercially available products such as "NeoCrystal 770" (manufactured by Nikka Chemical Co., Ltd., product name) and "Cellopol PC-300" (manufactured by Sanyo Chemical Industries, Ltd., product name) can be used.

[0464] The above - OP(O)(OX 1 )(OX 2 Examples of compounds having the following general formula include phosphate ester compounds. JPEG0007846437000012.jpg3336[where, X 1 or X 2 This is synonymous with the above, X 3 This represents an alkyl group with 1 to 22 carbon atoms.

[0465] As the phosphate ester compound mentioned above, phosphate monoesters, diesters, and triesters in which the alkyl ester portion has an alkyl group having 1 to 22 carbon atoms, as well as mixtures thereof, can be used.

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

[0467] For the phosphate ester compound, commercially available products such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name) can be used.

[0468] The pretreatment solution containing one or more compounds having the above-mentioned specific functional groups can, for example, be an aqueous solution of the compounds described above. The pretreatment solution may also contain acids, alkalis, surfactants, chelating agents, etc.

[0469] Methods for treating fibrous materials with the above-mentioned pretreatment solution include, for example, padding, immersion, spraying, and coating. For padding, for example, methods using padding equipment described on pages 396-397 of the Dictionary of Textile Dyeing and Processing (published in 1963 by Nikkan Kogyo Shimbun) and pages 256-260 of Color Dyeing Chemistry III (published in 1975 by Jikkyo Shuppan Co., Ltd.) can be used. For coating, for example, methods using coating machines described on pages 473-477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used. For immersion, for example, methods using batch-type dyeing machines described on pages 196-247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used, and liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, cheese dyeing machines, etc. can be used. Examples of spray treatments include air sprays that atomize the treatment solution using compressed air, and air sprays that use a hydraulic atomization system. The concentration of the treatment solution and the treatment conditions such as heat treatment after application can be adjusted as appropriate, taking into account the purpose, performance, and other conditions. If the pretreatment solution contains water, it is preferable to dry it to remove the water after it has been applied to the fiber material. There are no particular restrictions on the drying method, and either a dry heat method or a wet heat method may be used. There are no particular restrictions on the drying temperature, but for example, drying at room temperature to 200°C for 10 seconds to several days is sufficient. If necessary, after drying, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes.

[0470] Furthermore, if the fiber material is to be dyed, the pretreatment with the pretreatment solution may be performed before dyeing or in the same bath as the dyeing. However, if reducing soaping is performed, there is a risk that the compounds having the specific functional groups (e.g., phenolic polymer compounds, etc.) that have been adsorbed during the process may be removed. Therefore, it is preferable to perform the pretreatment after reducing soaping following dyeing.

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

[0472] In the functional group introduction step using the pretreatment solution, it is preferable to treat the material in such an amount that the amount of compound having the specified functional group attached is 1.0 to 7.0 parts by weight per 100 parts by weight of the fiber material. Within this range, a high level of both durable water repellency and texture can be achieved.

[0473] The pretreatment solution is preferably adjusted to a pH of 3-5. pH adjustment can be done using pH adjusting agents such as acetic acid or malic acid.

[0474] The pretreatment solution may also contain salt to effectively adsorb the compound having the above-mentioned specific functional group onto the fiber material through a salting-out effect. Examples of salts that can be used include sodium chloride. Examples include sodium carbonate, ammonium sulfate, and sodium sulfate.

[0475] In the functional group introduction step using the pretreatment solution, it is preferable to remove any compounds having the specified functional groups that have been excessively treated. One method of removal is washing with water. By performing sufficient removal, it is possible to suppress the inhibition of the development of water repellency in the subsequent water-repellent treatment, and in addition, the texture of the resulting textile product will be good. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fibers before contacting them with a hydrocarbon-based water repellent.

[0476] (ii) Examples of fibers in which the above-mentioned specific functional groups are directly introduced into the material constituting the fiber include cationic dyeable polyester (CD-PET).

[0477] From the viewpoint of obtaining good water repellency in the resulting textile product, the functional group-containing fibers preferably have a surface zeta potential of -100 to -0.1 mV, and more preferably -50 to -1 mV. The surface zeta potential of the fibers can be measured, for example, using the zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.). [Examples]

[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] <Testing Method> The examination procedure is as follows:

[0480] The following equipment was used for molecular weight analysis. Measurement by gel permeation chromatography (GPC) (hereinafter referred to as "GPC measurement"). Equipment: HLC-8420GPC EcoSEC Elite-WS (manufactured by Tosoh) Column: TSKgel SuperMultiporeHZ-M (manufactured by Tosoh) Column temperature: 40℃ Solvent: tetrahydrofuran Flow rate: 0.35mL / min Detector: Differential refractive index detector

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

[0482] 100 No wetting or water droplet adhesion was observed on the surface. 90 The surface did not become wet, but the adhesion of small water droplets was observed. 80 Wetting was observed on the surface in the form of small, individual water droplets. 70. Wetness was observed on half of the surface, and small, individual wet spots were seen penetrating the fabric. 50 Wetting was observed across the entire surface. 0. Wetting was observed throughout both the front and back surfaces.

[0483] [Light oil repellency test] 0.05 mL of the test solution was dropped onto the test cloth from a height of 0.6 cm. The above procedure was repeated, dropping 5 drops onto the cloth at 4.0 cm intervals. The absorption and shape of the oil droplets were observed after 30 ± 2 seconds to evaluate the mild oleophobicity. The test solution was prepared by mixing PEG-600 and oleic acid in a mass ratio of 9:1. The surface tension of this test solution was measured using an automatic surface tensimeter DY-300 (Kyowa Interface Science Co., Ltd.) and was found to be 35.7 mN / m. The oil repellency was evaluated according to the following criteria. A indicates the best oil repellency, and D indicates significantly low oil repellency. The evaluation value was taken from the results shown by 3 or more out of 5 drops. Intermediate values ​​(A-, B-, C+) were assigned depending on the condition.

[0484] A [Wet / Spread] Transparent (Not wet) [Shape of oil droplet] Rounded B [Wet / Stained] The edges and bottom are slightly discolored. [Shape of oil droplet] Rounded C [Wetness / Staining] Some staining is visible. [Shape of oil droplets] Contact angle is 35° or less D [Wet / Spread] Completely soaked [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 160N, and the seam slippage (mm) was measured. A smaller seam slippage value indicates better slip resistance, and it is most preferable that it is equivalent to untreated fabric, i.e., 2.0 mm or less.

[0486] [Preparation of raw materials] (Example of production of an aqueous dispersion containing a silicon-containing polymer) Manufacturing Example 1 In a 500 mL plastic container, 2.76 g of water-soluble glycol solvent was added 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 cationic dispersant, 2.14 g of sorbitan fatty acid ester, and 1.48 g of polyoxyethylene alkyl ether were added as dispersants. The mixture was heated to 70°C, stirred for 1 minute at 1000 rpm with a homomixer, and then emulsified and dispersed using ultrasound for 15 minutes. Next, this emulsion dispersion was transferred to a 200 mL four-necked flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux tube. After purging with nitrogen, 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 the polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a non-volatile content of 30%. GPC analysis of the polymer in this dispersion revealed a number-average molecular weight of 305,000.

[0487] Manufacturing Example 2 In a 500 mL plastic container, 2.76 g of water-soluble glycol solvent was added 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 cationic dispersant, 2.14 g of sorbitan fatty acid ester, and 1.48 g of polyoxyethylene alkyl ether were added as dispersants. The mixture was heated to 60°C, stirred with a magnetic stirrer at 800 rpm for 1 minute, and then emulsified and dispersed using ultrasound for 5 minutes. Next, this emulsion dispersion was transferred to a 200 mL four-necked flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux tube. After nitrogen purging, 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 the polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a non-volatile content of 30%. GPC analysis of the polymer in this dispersion revealed a number-average molecular weight of 1,400,000.

[0488] Manufacturing Example 3 In a 500 mL plastic container, 2.76 g of water-soluble glycol solvent was added 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 cationic dispersant, 2.14 g of sorbitan fatty acid ester, and 1.48 g of polyoxyethylene alkyl ether were added as dispersants. The mixture was heated to 70°C, stirred for 1 minute at 1000 rpm with a homomixer, and then emulsified and dispersed using ultrasound for 15 minutes. Next, this emulsion dispersion was transferred to a 200 mL four-necked flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux tube. After purging with nitrogen, 0.028 g of lauryl mercaptan was added and stirred. Then, 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 the polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a non-volatile content of 30%. GPC analysis of the polymer in this dispersion revealed a number-average molecular weight of 114,000.

[0489] Manufacturing Example 4 In a 500 mL plastic container, 1.38 g of water-soluble glycol solvent was added 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 cationic dispersant as a dispersant, 2.14 g of sorbitan fatty acid ester, and 1.48 g of polyoxyethylene alkyl ether were added. The mixture was heated to 70°C, stirred for 1 minute at 1000 rpm with a homomixer, and then emulsified and dispersed using ultrasound for 15 minutes. The emulsion dispersion was transferred to a 200 mL four-necked flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux tube. After nitrogen purging, 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 the polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a non-volatile content of 30%. GPC analysis of the polymer in this dispersion revealed a number-average molecular weight of 370,000.

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

[0492] Preparation Example 3 A 200 mL four-necked flask equipped with a stirring rod, thermometer, and reflux tube was charged with 12 g of methyl hydrogen silicone oil (SiH:SiCH3 molar ratio = 50:50 as measured by 1H NMR) and 0.02 g of platinum catalyst. Next, 36 g of 1-hexacocene was placed in a dropping funnel and added dropwise from the dropping funnel while maintaining the temperature at 70°C. After the addition was complete, the reaction was continued at 70°C for 3 hours. Infrared spectroscopy (IR) confirmed the disappearance of the SiH peak, 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 placed in a 250 mL glass container, heated to 75 °C, stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed using ultrasound for 10 minutes to obtain an aqueous dispersion of silicone polymer. Subsequently, this dispersion was diluted with pure water to prepare an aqueous dispersion with a non-volatile content of 30%.

[0493] Preparation Example 4 In a 500 mL plastic container, 30 g of water-soluble glycol solvent was added as an organic solvent, 120 g of pure water and 60 g of stearyl acrylate were added as liquid media, and 2.0 g of cationic emulsifier, 2.0 g of sorbitan fatty acid ester, and 6.0 g of polyoxyethylene alkyl ether were added as dispersants. The mixture was heated to 80°C, stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed using ultrasound for 15 minutes. The emulsion dispersion was transferred to a 500 mL four-necked flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux tube. After purging with nitrogen, 0.2 g of lauryl mercaptan was added and stirred. Then, 1.0 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 the polymer. Subsequently, pure water was added to prepare an aqueous dispersion with a non-volatile content of 30%.

[0494] Preparation Example 5 1. Synthesis of aliphatic polyisocyanate derivatives In a reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser, under a nitrogen atmosphere, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, trade name: Takenate 700), 0.25 parts by mass of 2,6-di(tert-butyl)-4-methylphenol (also known as dibutylhydroxytoluene, BHT, hindered phenol antioxidant), and 0.25 parts by mass of tetraphenyl-dipropylene glycol-diphosphite (organic phosphite ester, co-catalyst) were mixed. 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. Subsequently, the mixture was heated to 80°C and reacted for 3 hours, after which it was cooled to 60°C. Then, 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium·2-ethylhexanoate was added as an isocyanuration catalyst, and the reaction was carried out for 1.5 hours. Subsequently, 0.04 parts by mass of o-toluenesulfonamide was added to 100 parts by mass of HDI. This reaction mixture was then passed through a thin-film distillation apparatus (temperature 150°C, vacuum 93.3 Pa) and distilled until the remaining HDI monomer content was 0.5% or less, yielding an aliphatic polyisocyanate derivative (an isocyanurate derivative of hexamethylene diisocyanate). The obtained aliphatic polyisocyanate derivative had an isocyanate group content of 20.9% and an average isocyanate functional group count of 3.0.

[0495] 2. Manufacturing of hydrocarbon-based polyurethanes In a reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 100.20 g of the aliphatic polyisocyanate derivative, 67.60 g of Calcol 8098 (stearyl alcohol, manufactured by Kao Corporation) and 22.30 g of oleic alcohol were mixed and reacted under a nitrogen atmosphere at 110°C for 4 hours until the concentration of isocyanate groups reached 3.67%. Next, the reaction solution was cooled to 80°C, and 9.90 g of N-methyldiethanolamine was added as a cationic active hydrogen compound. The reaction was then carried out 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 the disappearance of the isocyanate group could be confirmed by infrared absorption spectroscopy. Next, 57.69 g of methyl erketone was added to the reaction mixture, the temperature was raised to 80°C, and the mixture was stirred until the reaction mixture was completely dissolved, after which it was cooled to 75°C. Subsequently, 18.96 g of acetic acid was added as an acid compound to neutralize the solution. Next, while maintaining the reaction solution at 75°C, 800.0g of deionized water heated to 70°C was gradually added to emulsify (internal emulsification). Next, the solvent was removed using an evaporator under reduced pressure at a water bath temperature of 60°C until the solid content concentration reached 20% by weight or more. Next, an aqueous dispersion containing polyurethane was obtained by adjusting the non-volatile content concentration, excluding acid compounds (acetic acid), to 20% using deionized water.

[0496] Preparation Example 6 A pressure reaction vessel was sealed and filled with 150g of paraffin wax (melting point 75°C), 350g of pure water, 4.5g of polyoxyethylene alkyl ether, and 3g of sorbitan fatty acid ester. The mixture was heated to 110-120°C while stirring, and then emulsified under high pressure for 30 minutes to prepare an aqueous dispersion of wax. Subsequently, pure water was added to prepare an aqueous dispersion of wax with a non-volatile content of 30%.

[0497] Comparative Manufacturing Example 1 In a 500 mL plastic container, 2.76 g of water-soluble glycol solvent was added 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, 2.25 g of cationic emulsifier, 2.14 g of sorbitan fatty acid ester, and 1.48 g of polyoxyethylene alkyl ether were added as dispersants. The mixture was heated to 70°C, stirred for 1 minute at 1000 rpm with a homomixer, and then emulsified and dispersed using ultrasound for 15 minutes. Next, this emulsion dispersion was transferred to a 200 mL four-necked flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux tube. After purging with nitrogen, 0.28 g of lauryl mercaptan was added and stirred. Then, 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 the polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a non-volatile concentration of 30%. GPC analysis of the polymer in this dispersion revealed a number-average molecular weight of 21,100.

[0498] Comparative Manufacturing Example 2 In a 500 mL plastic container, 30 g of a water-soluble glycol solvent was added 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, 2.14 g of sorbitan fatty acid ester, and 1.48 g of polyoxyethylene alkyl ether as dispersants. The mixture was heated to 70°C, stirred for 1 minute at 1000 rpm with a homomixer, and then emulsified and dispersed using ultrasound for 15 minutes. The emulsion dispersion was transferred to a 200 mL four-necked flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux tube. After purging with nitrogen, 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 the polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a non-volatile concentration of 30%. GPC analysis of the polymer in this dispersion revealed a number-average molecular weight of 350,000.

[0499] Example 1 A water-repellent composition was prepared by mixing an organosilicon polymer dispersion with tap water to obtain the composition shown in Table 1 (where the values ​​in the table indicate (weight %)). Polyester cloth, nylon cloth, and polyester / polyurethane (PU) cloth were immersed in this composition and then squeezed with a mangle. The treated cloth was then passed through a pin tenter at 170°C for 1 minute to dry and cure. The test fabrics treated in this manner were used to conduct tests for water repellency, light oil repellency, and slip resistance. The results are shown in Table 1.

[0500] Examples 2-15, Comparative Examples 1-7 Except for changing the formulation according to Table 1, test cloths were prepared in the same manner as in Example 1, and water repellency, light oil repellency, and slip resistance tests were conducted. The results are shown in Table 1.

[0501] [Table 1]

Claims

1. The following formula: HH ２ =C(-R ａ )-+-SiZ ３ [In the formula: R ａ This is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. X is -X 1 -X 2 - [In the formula, X1 is -C(=O)-O-, -O-C(=O)-, -C(=O)-NR'-, or -NR'-C(=O)- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms in each instance). X2 is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms. It is a group represented by ] Each Z is independent of the other, -O-SiZ ２ ３ And, Z ２ is, independently of one another, a hydrocarbon group having 1 to 3 carbon atoms or -OSiZ ２１ ３ and Z ２１ These are, independently, hydrocarbon groups having 1 to 3 carbon atoms. A polymer (A) containing repeating units derived from a silicon-containing monomer represented by [formula] and a dispersant (B) are provided. The polymer (A) contains 90% by weight or more of repeating units derived from the silicon-containing monomer, and A water-repellent composition wherein the number-average molecular weight of the polymer (A) is 60,000 or more and 4,000,000 or less.

2. The water-repellent composition according to claim 1, wherein the polymer (A) contains 96% by weight or more of repeating units derived from the silicon-containing monomer.

3. The water-repellent composition according to claim 1, wherein the number-average molecular weight of the polymer (A) is 2,000,000 or less.

4. The water-repellent composition according to claim 1, wherein the dispersant (B) comprises a cationic dispersant.

5. The water-repellent composition according to claim 1, comprising at least one compound (C) selected from the group consisting of vinyl polymers, isocyanate derivatives, waxes, and silicones.

6. The water-repellent composition according to claim 5, wherein the amount of polymer (A) in the water-repellent composition is 5% by weight to 95% by weight of the sum of the amount of polymer (A) and the amount of compound (C).

7. The water-repellent composition according to claim 5, wherein the compound (C) is a polymer containing repeating units derived from a hydrocarbon group-containing monomer having a hydrocarbon group having 2 to 40 carbon atoms.

8. The hydrocarbon group-containing monomer is of 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 Direct bond, divalent to tetravalent, carbon-1 hydrocarbon group, -C ６ H ４ -, -O-, -S-, -C(=O)-, -S(=O) ２ - and -NR Ｃ１ - (R Ｃ１ This is a divalent to tetravalent group composed of at least one selected from a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. k is between 1 and 3. R ｄ These are, independently, hydrocarbon groups having 2 to 40 carbon atoms. The water-repellent composition according to claim 7, wherein the monomer is represented by [the specified formula].

9. Z ２ Each of these is 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 Direct bond, divalent to tetravalent, carbon-1 hydrocarbon group, -C ６ H ４ -, -O-, -S-, -C(=O)-, -S(=O) ２ - and -NR Ｃ１ - (R Ｃ１ This is a divalent to tetravalent group composed of at least one selected from a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. k is between 1 and 3. R ｄ This is a hydrocarbon group having 2 to 40 carbon atoms. The compound (C) further comprises a polymer containing repeating units derived from a hydrocarbon group-containing monomer represented by , The water-repellent composition according to claim 1, wherein the amount of polymer (A) in the water-repellent composition is 5% by weight to 95% by weight of the sum of the amount of polymer (A) and the amount of compound (C).

10. R ａ is a hydrogen atom or a methyl group, X is -X １ -X ２ - [In the formula, X １ These are -C(=O)-O- and -O-C(=O)-, X ２ [This is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms] Z ２ Each of these is independently an alkyl group having 1 to 3 carbon atoms. The polymer (A) contains 97% by weight or more of repeating units derived from the silicon-containing monomer, and The number-average molecular weight of the polymer (A) is between 100,000 and 2,000,000. The water-repellent composition according to claim 1, wherein the dispersant (B) is a cationic dispersant.

11. A method for producing a textile product, comprising applying a water-repellent composition according to any one of claims 1 to 10 to a textile substrate.

12. Before applying the water-repellent composition to the fiber substrate, the fibers -SO ３ M １ (In the formula, M １ A monovalent group represented by (where indicates a monovalent cation), -COOM ２ (In the formula, M ２ (where represents a monovalent cation), and -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ A method for producing a textile product according to claim 11, comprising the step of imparting one or more functional groups selected from the group consisting of monovalent groups (each independently representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

13. A textile product having a water-repellent composition according to any one of claims 1 to 10 attached to a fibrous base material.

14. -SO ３ M １ (In the formula, M １ A monovalent group represented by (where indicates a monovalent cation), -COOM ２ (In the formula, M ２ (where represents a monovalent cation), and -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ The textile product according to claim 13, wherein a compound having one or more functional groups selected from the group consisting of monovalent groups (each independently representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) is attached to it.

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