Polymer, water repellent, fiber product, and method for producing fiber product

Abstract

To provide a polymer that can impart superior water repellency and chalk mark resistance to a substrate.SOLUTION: Disclosed is a polymer for use in a water repellent for fibers, which includes a repeating unit that is derived from a monomer (1) represented by formula (1-1) or formula (1-2): CRaRb=C(-Rc)-X-CY3-nZn (1-1), CRaRb=C(-Rc)-X-NY2-nZn (1-2). [In each formula: Ra, Rb, and Rc each independently represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, X represents a single bond or a divalent group, each Y independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n represents an integer of 1 or 2, and each Z independently represents -Z1-SiZ23, Z1 represents a single bond or a divalent group, and each Z2 independently represents -(O-Si(-OSiZ213)2)p-O-SiZ223].SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a polymer, a water repellent, a textile product, and a method for manufacturing a textile product.

Background Art

[0002] Development of non-fluorine-based water repellents is underway as water repellents for imparting water repellency to a base material (especially a textile product).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Patent Document 1 discloses that a composition in which a silicone-containing copolymer containing a structural unit derived from an (meth)acrylic acid alkyl ester monomer is dissolved in a solvent can be treated on an object to be treated such as a textile product to impart good chalk mark resistance. However, the water repellency is not sufficient.

[0005] An object of the present disclosure is to provide a polymer capable of imparting good water repellency and chalk mark resistance to a base material.

Means for Solving the Problems

[0006] The present disclosure includes the following aspects: [Item 1] A polymer used for a water repellent for fibers, which is represented by the following formula (1-1) or formula (1-2): CR a R b =C(-R c )-X-CY 3-n Z n (1-1) CR a R b =C(-R c)-X-NY 2-n Z n (1 - 2) [In each formula: R a 、R b 、and R c is, independently of each other, a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, X is a single bond or a divalent group, Y is, independently of each other, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 or 2, Z is, independently of each other, -Z 1 -SiZ 2 3, Z 1 is a single bond or a divalent group, Z 2 is, independently of each other -(O - Si(-OSiZ 21 3)2) p -O - SiZ 22 3, Z 21 is, independently of each other, a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 211 3, Z 211 is, independently of each other, a hydrocarbon group having 1 to 10 carbon atoms, Z 22 is, independently of each other, a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 221 3, Z 221 is, independently of each other, a hydrocarbon group having 1 to 10 carbon atoms, p is an integer of 0 to 196.] A polymer used in a water - repellent agent for fibers containing a repeating unit derived from the monomer (1) represented by the formula. [Item 2]X is a divalent group composed of one or more selected from the group consisting of X 1 and X 2 and is composed of one or more selected from the group consisting of, X 1is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -NR’-, and -C(OR’)R’- (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). X 2 is a direct bond or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent, the polymer according to item 1. [Item 3] X is -X 1 -X 2 -, the polymer according to item 2. [Item 4] Z 1 is 11 and Z 12 is a divalent group composed of one or more selected from the group consisting of, Z 11 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -NR’-, and -C(OR’)R’- (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). Z 12 is a direct bond or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent, the polymer according to any one of items 1 to 3. [Item 5] Z 1 is a direct bond or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent, the polymer according to item 4. [Item 6] The polymer according to any one of items 1 to 5, wherein n is 1. [Item 7] At least two of the three Z in the OSiZ 21 3 21 are -OSiZ 21 , the polymer according to any one of items 1 to 6. 211 is [Item 8] At least two of the three Z in the SiZ 22 3 22 are -OSiZ 22 is 221 , the polymer according to any one of claims 1 to 7. [Item 9] The polymer according to any one of Items 1 to 8, further comprising a repeating unit derived from a hydrophobic monomer (2) having a hydrocarbon group with 2 to 40 carbon atoms. [Item 10] The polymer according to Item 9, wherein the hydrocarbon group in the hydrophobic monomer (2) is a linear alkyl group having 10 or more carbon atoms. [Item 11] The hydrophobic monomer (2) is represented by the following formula: CH2=C(-R b )-C(=O)-R c -(R d ) k (2) [In the formula, R b is a hydrogen atom, a monovalent organic group or a halogen atom, R c is a direct bond, a hydrocarbon group with 1 to 4 carbon atoms having 2 to 4 valences, -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2- and -NR C1 -(R C1 is a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms) and is a divalent to tetravalent group composed of at least one selected from the above, k is 1 to 3, R d is a hydrocarbon group with 2 to 40 carbon atoms.] The polymer according to Item 9 or 10, which is a monomer represented by the above formula. [Item 12] The polymer according to any one of Items 9 to 11, wherein the content of the hydrophobic monomer (2) is 20% by weight or more based on the polymer. [Item 13] The polymer according to Item 12, wherein the content of the monomer unit (1) is 0.5% by weight or more based on the polymer. [Item 14] The polymer according to Item 13, wherein the weight ratio of the monomer unit (1) represented by the monomer unit (1) / the monomer unit (2) in the polymer is 0.005 to 0.40. [Item 15] The polymer according to any one of Items 1 to 14, which is non-fluorine-based. [Item 16] Monomer (1) is represented by the above formula: CR a R b =C(-R c )-X-NY 2-n Z n(1-2) and R a and R b are each independently a hydrogen atom, R c are each independently an alkyl group having 1 to 3 carbon atoms, X is -C(=O)-O-(CH2) r - or -C(=O)-NR'-(CH2) r -(wherein R' is each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). r is each independently an integer from 1 to 22, the polymer according to item 1. [Item 17] Y is each independently an alkyl group having 1 to 3 carbon atoms, n is 1, Z 1 is -(CH2) q -, q is an integer from 1 to 22, p is 0, Z 22 is each independently an alkyl group having 1 to 3 carbon atoms or -OSiZ 221 3, Z 221 is each independently an alkyl group having 1 to 3 carbon atoms, the polymer according to item 1. [Item 18] The monomer (1) has the formula: CR a R b =C(-R c )-X-NY 2-n Z n (1-2) and R a and R b are each independently a hydrogen atom, R c are each independently an alkyl group having 1 to 3 carbon atoms, X is -C(=O)-O-(CH2) r - or -C(=O)-NR'-(CH2) r -(wherein R' is each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). r is, independently of one another, an integer from 1 to 22, Y is, independently of one another, an alkyl group having 1 to 3 carbon atoms, n is 1, Z 1 is -(CH2) q -. q is an integer from 1 to 22, p is 0, Z 22 is, independently of one another, an alkyl group having 1 to 3 carbon atoms or -OSiZ 221 3, Z 221 is, independently of one another, an alkyl group having 1 to 3 carbon atoms, the polymer according to item 1. [Item 19] A composition comprising the polymer according to any one of items 1 to 18 and an emulsifier. [Item 20] The composition according to item 19, comprising water. [Item 21] A water-repellent agent comprising the polymer used for the water-repellent agent for fibers according to any one of items 1 to 18, or the composition according to item 19 or 20. [Item 22] A process for producing the water-repellent agent according to item 21, comprising a step of reacting monomer (1) in a medium containing at least one selected from the group consisting of urethane, paraffin wax, silica, and silicone to obtain a polymer. [Item 23] A water-repellent fiber product having adhered thereto the polymer according to any one of items 1 to 18. [Item 24] The fiber substrate 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 2The water-repellent fiber product according to item 23, to which a compound having one or more functional groups selected from the group consisting of monovalent groups represented by (each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) is attached. [Item 25] A method for producing a water-repellent fiber product, which includes applying the water-repellent agent according to item 21 to a fiber substrate. [Item 26] Before applying the water-repellent agent to the fiber substrate, -SO3M 1 (In the formula, M 1 represents a monovalent cation) a monovalent group represented by, -COOM 2 (In the formula, M 2 represents a monovalent cation) a monovalent group represented by, and -O-P(O)(OX 1 )(OX 2 (In the formula, X 1 and X 2 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) a method for producing a water-repellent fiber product according to item 25, which includes a step of imparting one or more functional groups selected from the group consisting of monovalent groups represented by.

Advantages of the Invention

[0007] The polymer in the present disclosure can impart good water repellency and resistance to chalking marks to a substrate.

Modes for Carrying Out the Invention

[0008] <Definition of Terms> As used herein, the term "n-valent group" means a group having n bonds, that is, a group forming n bonds. Further, the "n-valent organic group" means an n-valent group containing carbon, and the "organic group" means a group containing carbon. Such an organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. The 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 the hydrocarbon group.

[0009] As used herein, the term "hydrocarbon group" means a group containing carbon and hydrogen and is a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group is not particularly limited, and may be, for example, a C1-20 hydrocarbon group, such as 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. Further, the hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents.

[0010] In this specification, regardless of whether the expression "independently at each occurrence", "independently of each other", "independently of one another" or a similar expression is explicitly described, unless there is a description to the contrary, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition is applied independently for each occurrence.

[0011] The chemical structures described in this specification should be understood not to include chemical structures that are recognized by those skilled in the art as chemically impossible or extremely unstable.

[0012] <Polymer> The polymer of the present disclosure is a polymer used as a water repellent for fibers and has the following formula (1-1) or formula (1-2): CR a R b =C(-R c )-X-CY 3-n Z n (1-1) CR a R b =C(-R c )-X-NY 2-n Z n (1-2) [In each formula: R a , R b , and R c are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, X is a single bond or a divalent group, Y is, independently of one another, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 or 2, Z is, independently of one another, -Z 1 -SiZ 2 is 3, Z 1 is a single bond or a divalent group, Z 2 is, independently of one another -(O-Si(-OSiZ 21 3)2) p -O-SiZ 22 is 3, Z 21 is, independently of one another, a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 211 is 3, Z 211 is, independently of one another, a hydrocarbon group having 1 to 10 carbon atoms, Z 22 is, independently of one another, a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 221 is 3, Z 221 is, independently of one another, a hydrocarbon group having 1 to 10 carbon atoms, p is an integer from 0 to 196.] It contains a repeating unit derived from the monomer (1) represented by

[0013] By having the above characteristics, the polymer of 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 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, and a water resistant. The liquid repellent agent in the present disclosure can preferably impart oil resistance (oil repellency) and / or water resistance (water repellency) to a substrate, and can preferably impart both oil resistance and water resistance, for example.

[0014] By having the above characteristics, the polymer of the present disclosure can impart chalk mark resistance to a substrate (for example, a fiber substrate, a paper substrate).

[0015] The polymer of the present disclosure may be non-fluorinated. Specifically, the polymer 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.

[0016] (1) Monomer The polymer of the present disclosure contains a repeating unit derived from monomer (1). Monomer (1) is represented by the following formula (1-1) or formula (1-2). CR a R b =C(-R c )-X-CY 3-n Z n (1-1) CR a R b =C(-R c )-X-NY 2-n Z n (1-2)

[0017] [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. R a may be a hydrogen atom.

[0018] [R b R b 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. R b may be a hydrogen atom.

[0019] [R c R c 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, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R c may be a hydrogen atom.​​​

[0020] [X] X is a single bond or a divalent group. X is preferably a divalent group.

[0021] X is X 1 and X 2 is a divalent group composed of one or more selected from the group consisting of X 1 is a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, and -C(OR')R'-(wherein R' is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (for example, 1 to 5, 1 to 3, or 1 carbon atoms)).) is a group composed of one or more selected from the group consisting of X 2 may be a direct bond or a divalent hydrocarbon group having 1 to 22 carbon atoms which may have a substituent.

[0022] 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.

[0023] [X 1 X 1 is a non-hydrocarbon linker.

[0024] X 1 is a direct bond or a divalent group. X 1 is preferably not only a direct bond.

[0025] X 1 The molecular weight of may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less. X 1 The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.

[0026] ​ X 1 is -O-, -C(=O)-, -S(=O)2-, -NR’-, and -C(OR’)R’- (wherein R’ is independently at each occurrence composed of one or more selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms). X 1 Examples of a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-, -NR’-C(=O)-O-, -NR’-C(=O)-NR’-, -C(=O)-, -C(=O)-O-, -C(=O)-NR’-, -SO2-, -SO2NR’-, -C(OR’)R’-, -C(OR’)(-)2 etc. (wherein R’ is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).) are included.

[0027] 〔X 2 〕 X 2 is a direct bond or a divalent hydrocarbon group which may have a substituent.

[0028] X 2 may have 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more carbon atoms. X 2 may have 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 carbon atoms.

[0029] The divalent hydrocarbon group may be a divalent aliphatic hydrocarbon group or a divalent hydrocarbon aromatic ring. The aliphatic hydrocarbon group may be a cyclic, branched, or straight-chain hydrocarbon group. The divalent aliphatic hydrocarbon group may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more, and 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.

[0030] X 2 The hydrocarbon group in may have a substituent. Examples of the substituent include -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein, R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0.

[0031] X 2 Specific examples of include -(CH2) q -. q is an integer from 1 to 22. q may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more. q may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, or 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0032] Specific examples of the divalent hydrocarbon aromatic ring include groups obtained by removing 2 to 4 hydrogens from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms in the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may also be 4 or less, 3 or less, or 2.

[0033] The divalent hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R’, -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon aromatic ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0034] 〔Examples of X〕 Examples of X include -X 1 -, -X 1 -X 2 -, -X 1 -X 2 -X 1 -, -X 1 -X 2 -X 1 -X 2 -, -X 2 -, -X 2 -X 1 -, -X 2 -X 1 -X 2 -, -X 2 -X 1 -X 2 -X 1 -, etc. are included. Preferred examples of X include -X 1 -X 2 -, -X 2 - is included.

[0035] Examples of X include -O-(CH2) r -, -O-C(=O)-(CH2) r -, -O-C(=O)-O-(CH2) r -, -O-C(=O)-NR’-(CH2) r -、 -NR’-(CH2) r -、 -NR’-C(=O)-(CH2) r -、 -NR’-C(=O)-O-(CH2) r -、 -NR’-C(=O)-NR’-(CH2) r -、 -C(=O)-(CH2) r -、 -C(=O)-O-(CH2) r -、 -C(=O)-NR’-(CH2) r -、 -SO2-(CH2) r -、 -SO2NR’-(CH2) r -、 -C(OR’)R’-(CH2) r -、 -C(OR’)(-(CH2) r -)2 etc. (In the formula, R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).) include. r is an integer from 1 to 22. r may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more. q may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, or 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0036] Examples of X include -C(=O)-O-(CH2) r - or -C(=O)-NR’-(CH2) r (wherein, each R’ is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.), and each r is independently an integer from 1 to 22, 1 to 10, or 1 to 4.

[0037] X may be a hydrocarbon group having 1 to 22 carbon atoms with or without a substituent. Preferably, X may be a hydrocarbon group having 1 to 22 carbon atoms with or without a substituent. The number of carbon atoms of the hydrocarbon group of X may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more. The number of carbon atoms of the hydrocarbon group of X 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.

[0038] Specific examples of X include -(CH2) q - and the like. q is an integer from 1 to 22. q may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more. q may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, or 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0039] [Y] Each Y is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Y is preferably a branched or linear (preferably long-chain linear) hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The -CH3 group has a lower surface free energy than -CH2- and is more likely to show liquid repellency. Therefore, a structure with many branches and many -CH3 groups is preferred. On the other hand, a long-chain alkyl group of a certain length shows high liquid repellency due to its crystallinity. Thus, a branched hydrocarbon group (e.g., a branched alkyl group), particularly a t-butyl group or an isopropyl group, a multi-branched structure group, or a long-chain hydrocarbon group (or a long-chain linear hydrocarbon group), e.g., an alkyl group, may be used.

[0040] The number of carbon atoms of the hydrocarbon having 1 to 10 carbon atoms of Y may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. The number of carbon atoms of the hydrocarbon having 1 to 10 carbon atoms of Y may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0041] For example, Y is -(CH2)n It may be -CH3. n may be from 0 to 9, may be 0 or more, 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more, and may be 9 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0042] Y may be an alkyl group having 1 to 3 carbon atoms, preferably may be a methyl group.

[0043] [n] n means the number of Z groups in formulas (1-1) and (1-2). n is an integer of 1 or 2.

[0044] [Z] Z are each independently -Z 1 -SiZ 2 is 3. Z is a group having a siloxane bond.

[0045] [Z 1 Z 1 is a single bond or a divalent group. Z 1 is preferably a divalent group.

[0046] Z 1 is Z 11 and Z 12 and is a divalent group composed of one or more selected from the group consisting of Z 11 is a direct bond, -O-, -C(=O)-, -C(=NR'')-, -S-, -S(=O)2-, -NR'', and -C(OR'')R''- (wherein R'' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (for example, 1 to 5 carbon atoms, 1 to 3 carbon atoms, or 1 carbon atom)). It may be a group composed of one or more selected from the group consisting of.

[0047] Z 1 ​The molecular weight of 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 Y 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.

[0048] (Z 11 ) Z 11 is a non-hydrocarbon linker.

[0049] Z 11 is a direct bond or a divalent group. Z 11 Preferably, it is not only a direct bond.

[0050] Z 11 The molecular weight of may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less. X 1 The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.

[0051] Z 11 is -O-, -C(=O)-, -S(=O)2-, -NR’-, and -C(OR’)R’- (wherein R’ is independently selected from the group consisting of a hydrogen atom and one or more selected from the group consisting of 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms) at each occurrence. Z 11 Examples of include a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-, -NR’-C(=O)-O-, -NR’-C(=O)-NR’-, -C(=O)-, -C(=O)-O-, -C(=O)-NR’-, -SO2-, -SO2NR’-, -C(OR’)R’-, -C(OR’)(-)2, etc. (In the formula, R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) include.

[0052] (Z 12 ) Z 12 is a direct bond or a hydrocarbon group which may have a substituent.

[0053] Z 12 The number of carbon atoms of may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, or 8 or more. The number of carbon atoms of Z 12 may be 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, or 5 or less.

[0054] Z 12 The hydrocarbon group in may have a substituent. Examples of the substituent include -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (In the formula, R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0.

[0055] Z 12 Specific examples of include -(CH2) q -. q is an integer from 1 to 22. q may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more. q may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, or 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0056] (Example of Z 1 ) Z 1 Examples of include -Z11 -, -Z 11 -Z 12 -, -Z 11 -Z 12 -Z 11 -, -Z 11 -Z 12 -Z 11 -Z 12 -, -Z 12 -, -Z 12 -Z 11 -, -Z 12 -Z 11 -Z 12 -, -Z 12 -Z 11 -Z 12 -Z 11 -, etc. may be mentioned. Z 1 Preferred examples of are -Z 11 -Z 12 -, -Z 12 - may be mentioned.

[0057] Z 1 may be a hydrocarbon group having 1 to 10 carbon atoms which may be directly bonded or may have a substituent. Preferably, Z 1 may be a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. Z 1 The number of carbon atoms of the hydrocarbon group of may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. Z 1 The number of carbon atoms of the hydrocarbon having 1 to 10 carbon atoms may be 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0058] Z 1 Specific examples of include -(CH2) q - may be mentioned. q is an integer from 1 to 22. q may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 9 or more, 11 or more, or 13 or more. q may be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, or 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0059] 〔Z 2 〕 Z 2 are each independently -(O-Si(-OSiZ 21 3)2) p -O-SiZ 22 is 3.

[0060] (Z 21 ) Z 21 is, independently of one another, a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 211 3.

[0061] Z 21 The hydrocarbon having 1 to 10 carbon atoms may have 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more carbon atoms. Z 21 The hydrocarbon having 1 to 10 carbon atoms may have 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less carbon atoms. Z 21 may be a methyl group.

[0062] In the above OSiZ 21 Among the three Z in 3 21 At least two of the Z 21 may be -OSiZ 211 In the above OSiZ 21 Among the three Z in 3 21 All of the Z 21 may be either -OSiZ 211 or a hydrocarbon group having 1 to 10 carbon atoms, and one Z 21 may be -OSiZ 211

[0063] (Z 211 ) Z 211 is, independently of one another, a hydrocarbon group having 1 to 10 carbon atoms. Z 211 The hydrocarbon having 1 to 10 carbon atoms may have 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more carbon atoms. Z 211 The hydrocarbon having 1 to 10 carbon atoms may have 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less carbon atoms. Z 211 may be a methyl group.

[0064] (Z 22 ) Z 22 is, independently of one another, a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 221 3.

[0065] Z 22 The hydrocarbon having 1 to 10 carbon atoms may have 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more carbon atoms. Z 22 The hydrocarbon having 1 to 10 carbon atoms may have 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less carbon atoms. Z 22 may be an alkyl group having 1 to 3 carbon atoms. Z 22 may be a methyl group.

[0066] The above OSiZ 22 Among the three Zs in 3 22 at least two Zs 22 may be -OSiZ 221 . The above OSiZ 22 Among the three Zs in 3 22 all of the Zs 22 may be either -OSiZ 221 or a hydrocarbon group having 1 to 10 carbon atoms, and one Z 22 may be -OSiZ 221 .

[0067] (Z 221 ) Z 221 is, independently of one another, a hydrocarbon group having 1 to 10 carbon atoms. Z 221 The hydrocarbon having 1 to 10 carbon atoms may have 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more carbon atoms. Z 221 The hydrocarbon having 1 to 10 carbon atoms may have 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less carbon atoms. Z 221 may be an alkyl group having 1 to 3 carbon atoms. Z 221 may be a methyl group.

[0068] [p] p is an integer from 0 to 196. p may be 0 or more, 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, or 100 or more. p may be 196 or less, 190 or less, 180 or less, 170 or less, 160 or less, 150 or less, 140 or less, 130 or less, 120 or less, 110 or less, or 100 or less.

[0069] The total value of p in formula (1-1) or (1-2) should not exceed 196.

[0070] In one aspect, p is 0.

[0071] The monomer (1) is preferably a monomer represented by formula (1-2).

[0072] The terminal part of the monomer (1) of the present disclosure may include a trialkylsiloxy group-containing structure in which a trialkylsiloxy group (-OSiR Si 3) is bonded to an Si atom (R Si is a hydrocarbon group having 1 to 10 carbon atoms, which will be described in detail below.).

[0073] The Si atom of the terminal part mentioned above does not mean the Si atom constituting the trialkylsiloxy group (-OSiR Si 3), but means the Si atom adjacent to and bonded to the trialkylsiloxy group (-OSiR Si 3). Note that an alkyl group (R Si ) may be bonded to the Si atom.

[0074] The number of trialkylsiloxy groups (-OSiR Si 3) bonded to the Si atom at the terminal part of the monomer (1) of the present disclosure is an integer from 1 to 3. Note that the terminal part of the monomer (1) of the present disclosure means the terminal part on the Z side in the above formula and is a part located in Z.

[0075] Specifically, the terminal part of the monomer (1) of the present disclosure has the following formula: -Si(-OSiR Si 3)X R Si 3-X [wherein: R Si is each independently a hydrocarbon group having 1 to 10 carbon atoms, x is an integer from 1 to 3.] It may contain a structure represented by.

[0076] R Si is a hydrocarbon group having 1 to 10 carbon atoms. R Si The hydrocarbon having 1 to 10 carbon atoms of R Si may have 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more carbon atoms. R Si may be an alkyl group having 1 to 3 carbon atoms. R Si may be a methyl group.

[0077] x is an integer from 1 to 3. x may be 1 or more, 2 or more, and may be 3 or less, 2 or less, or 1 or less.

[0078] As the trialkylsiloxy group (-OSiR Si 3) bonded to the Si atom at the terminal site of the monomer (1), -OSiZ 221 3 described above can be mentioned.

[0079] [(1) Examples of monomers] The monomer (1) has the following formula: CH2=CCH3-C(=O)-R a6 -(CH2) q -N(-Y)-(CH2) r -SiZ 3 3 [wherein: R a6 is -O- or -NH-, q is an integer from 1 to 10, r is an integer from 1 to 10, Y is each independently an alkyl group having 1 to 3 carbon atoms, Z3 is, independently, -O-SiZ 33 is 3, Z 33 is, independently, an alkyl group having 1 to 10 carbon atoms or -OSiZ 331 is 3, Z 331 is, independently, an alkyl group having 1 to 10 carbon atoms.] It may be a monomer represented by

[0080] R a6 is -O- or -NH-, preferably -O-.

[0081] q is an integer from 1 to 10. q may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and may also be 10 or less, 9 or less, 8 or less, 6 or less, 5 or less.

[0082] r is an integer from 1 to 10. r may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and may also be 10 or less, 9 or less, 8 or less, 6 or less, 5 or less.

[0083] Y is, independently, an alkyl group having 1 to 3 carbon atoms, preferably a methyl group.

[0084] Z 3 is, independently, -O-SiZ 33 is 3.

[0085] Z 33 is, independently, an alkyl group having 1 to 10 carbon atoms or -OSiZ 331 is 3. Z 33 The number of carbon atoms of the hydrocarbon having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.

[0086] Z 331 is, independently, an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.

[0087] [Examples of the monomer (1)] Examples of the polymer include, but are not limited to, compounds represented by the following formula. In the following formula, TMS means -Si(CH3)3. TIFF0007712587000001.tif41126

[0088] TIFF0007712587000002.tif4169

[0089] The monomer (1) of the present disclosure can be produced, for example, in accordance with the content described in WO2020 / 142441. As the monomer (1) of the present disclosure, commercially available products may be used.

[0090] (2) Hydrophobic monomer The polymer of the present disclosure may further include a repeating unit derived from a hydrophobic monomer (2) having a hydrocarbon group with 2 to 40 carbon atoms.

[0091] The hydrocarbon group of the monomer (2) 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 is branched or linear, more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms of the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, 14 or more, or 16 or more. The number of carbon atoms of 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, preferably 30 or less, 25 or less, or 20 or less.

[0092] The monomer (2) may contain an amide group, a urea group, or a urethane group. The hydrocarbon monomer may be a combination of a hydrocarbon monomer having an amide group, a urea group, or a urethane group and a hydrocarbon monomer having no amide group, urea group, or urethane group. By including such a group in the monomer (2), the effects of the present disclosure can be achieved well.

[0093] The hydrophobic monomer (2) has the following formula: CH2=C(-R b )-C(=O)-R c -(R d ) k (2) [In the formula, R b is a hydrogen atom, a monovalent organic group, or a halogen atom, R c is a direct bond, a divalent to tetravalent hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2-, and -NR C1 -(R C1 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms) and is a divalent to tetravalent group composed of at least one selected from the above, k is 1 to 3, R d is a hydrocarbon group having 2 to 40 carbon atoms.] It is a monomer represented by.

[0094] [R b R b is a hydrogen atom, a monovalent organic group, or a halogen atom.

[0095] R b may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Examples of R b are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. R b is preferably a hydrogen atom, a methyl group, or a chlorine atom. R b is more preferably a methyl group. When R b is a methyl group, higher liquid repellency can be obtained.​b may be a hydrogen atom, particularly from the perspective of reactivity.

[0096] [R c R c is a direct bond, a C1 hydrocarbon group with a valence of 2 to 4, -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2-, and -NR C1 -(R C1 which is a hydrogen atom or a C1-C4 hydrocarbon group) and is a divalent to tetravalent group composed of at least one or more selected from them, and k is 1 to 3.

[0097] R c is preferably a divalent group. Examples of the C1 hydrocarbon group with a valence of 2 to 4 are -CH2-, -CH= with a branched structure, and -C≡ with a branched structure.

[0098] R c is -R Y -, -R Y -R Y -, -R Y -C(=O)-, -C(=O)-R Y -, -R Y -C(=O)-R Y -, -R Y -R X -, -R Y -R Y -R Y -, -R Y -R X -R Y -C(=O)-, -R Y -R X -C(=O)-R Y -, -R Y -R X -R Y -C(=O)-R Y -, or -R Y -R X -R Y -R X - [In the formula, each R Y is independently a direct bond, -O-, -NR C11 -(R C11 ​is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or -S(=O)2-, R X is -(CH2) m -(where m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l -(where l is independently an integer of 0 to 5, and -C6H4- is a phenylene group).] may be. R c is preferably not only a divalent hydrocarbon group.

[0099] R c Specific examples of are -O-, -NH-, -O-C(=O)-, -NH-C(=O)-, -O-C(=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 -O-C(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -O-C(=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 -NH-S(=O)2-, -NH-(CH2) m-S(=O)2-NH--NH-(CH2) m -O-C(=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-、 or -NH-(CH2) m -NH-C6H4- [wherein, m is an integer of 1 to 5, particularly 2 or 4].

[0100] R c is -O-, -NH-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -NH-C(=O)-NH- [wherein, m is an integer of 1 to 5, particularly 2 or 4]. is preferably. R c is -O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, or -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m-S(=O)2-NH-, especially -O-(CH2) m -NH-C(=O)- is more preferable.

[0101] [R d R d is a hydrocarbon group having 2 to 40 carbon atoms.

[0102] R d is preferably a branched or linear (preferably long-chain linear) hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The -CH3 group has a lower surface free energy than the -CH2- group and is more likely to exhibit liquid repellency. Therefore, a structure with many branches and many -CH3 groups is preferred. On the other hand, a long-chain alkyl group of a certain length exhibits high liquid repellency due to its crystallinity. Thus, a branched hydrocarbon group (e.g., a branched alkyl group), particularly a t-butyl group or an isopropyl group, a multi-branched structure group, or a long-chain hydrocarbon group (or a long-chain linear hydrocarbon group), e.g., an alkyl group, may be used. R d The number of carbon atoms of may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 11 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more. R d The number of carbon atoms of may be 40 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 12 or less.

[0103] [k] k is 1, 2, or 3. When R c has a tetravalent hydrocarbon group having 1 carbon atom, etc., k = 3. R c has a trivalent hydrocarbon group having 1 carbon atom, etc., k = 2. R c when it does not have a trivalent and tetravalent hydrocarbon group having 1 carbon atom (e.g., when R c has a divalent hydrocarbon group having 1 carbon atom (-CH2-) (e.g., 1 to 6), k = 1.

[0104] Examples of the monomer (2) are (a1) formula: CH2=C(-X​a1 )-C(=O)-Y a1 -R a1 [In the formula, R a1 is a hydrocarbon group having 6 to 40 carbon atoms, X a1 is a hydrogen atom, a monovalent organic group or a halogen atom, Y a1 is -O- or -NH-.] The monomer represented by, and (a2) Formula: CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Y a22 -R a2 ) n [In the formula, R a2 are each independently a hydrocarbon group having 6 to 40 carbon atoms, X a2 is a hydrogen atom, a monovalent organic group or a halogen atom, Y a21 is -O- or -NH-, Y a22 are each independently a group composed of at least one selected from a direct bond, -O-, -C(=O)-, -S(=O)2-, -NH- or -CH2-, Z is a direct bond, or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, n is 1 or 2.] It is a monomer represented by.

[0105] (a1) Monomer Monomer (a1) has the formula: CH2=C(-X a1 )-C(=O)-Y a1 -R a1 [In the formula, R a1 is a hydrocarbon group having 6 to 40 carbon atoms, X a1 is a hydrogen atom, a monovalent organic group or a halogen atom, Y a1 is -O- or -NH-.] It is a compound represented by

[0106] The monomer (a1) is Y a1 is a long-chain acrylate monomer in which Y a1 is -NH-, or a long-chain acrylamide monomer in which Y R a1 is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. In R a1 , the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26, particularly 18 to 22. X a1 may be a hydrogen atom, a halogen other than a methyl group and a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. It is preferably a hydrogen atom, a methyl group or a chlorine atom.

[0107] Preferred specific examples of the long-chain acrylate monomer are lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, icosyl α-chloroacrylate, behenyl α-chloroacrylate. Preferred specific examples of the long-chain acrylamide monomer are stearyl (meth)acrylamide, icosyl (meth)acrylamide, behenyl (meth)acrylamide.

[0108] (a2) monomer The monomer (a2) is a monomer different from the monomer (a1). The monomer (a2) 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-. The monomer (a2) has the formula: CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Y a22 -R a2 ) n [wherein, R a2is, independently of one another, a hydrocarbon group having 6 to 40 carbon atoms, X a2 is a hydrogen atom, a monovalent organic group or a halogen atom, Y a21 is -O- or -NH-, Y a22 is, independently of one another, a group composed of at least one selected from a direct bond, -O-, -C(=O)-, -S(=O)2-, -NH- or -CH2-, Z is a direct bond, or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, n is 1 or 2.] It may be a compound represented by. Y a22 And / or Z may not be a direct bond. Y a22 And Z may not be a direct bond at the same time.

[0109] R a2 is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. R a2 In, the number of carbon atoms of the hydrocarbon group is preferably 12 to 30, for example 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22.

[0110] X a2 may be a hydrogen atom, a halogen other than a methyl group and a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. It is preferably a hydrogen atom, a methyl group or a chlorine atom.

[0111] Y a22 is -Y’-, -Y’-Y’-, -Y’-C(=O)-, -C(=O)-Y’-, -Y’-C(=O)-Y’-, -Y’-R’-, -Y’-R’-Y’-, -Y’-R’-Y’-C(=O)-, -Y’-R’-C(=O)-Y’-, -Y’-R’-Y’-C(=O)-Y’-, or -Y’-R’-Y’-R’- [wherein Y’ is, independently of one another, a direct bond, -O-, -NH- or -S(=O)2-, R’ is -(CH2) m-(where m is an integer from 1 to 5), a linear hydrocarbon group having an unsaturated bond with 1 to 5 carbon atoms, a hydrocarbon group having a branched structure with 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l -(where l is independently an integer from 0 to 5 and -C6H4- is a phenylene group).] It may be.

[0112] Y a22 Specific examples of are direct bond, -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -O-C(=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 -O-C(=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- [wherein, m is an integer of 1 to 5.] is.

[0113] Y a22 is preferably -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-. Y a22 is more preferably -NH-C(=O)-, -C(=O)-NH-, -O-C(=O)-NH-, -NH-C(=O)-O- or -NH-C(=O)-NH-. Y a22 may not be a direct bond.

[0114] Z is a direct bond, or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a linear structure or a branched structure. The number of carbon atoms of Z is preferably 2 to 4, particularly 2. Specific examples of Z are a direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH= having a branched structure, -CH2(CH-)CH2- having a branched structure, -CH2CH2CH= having a branched structure, -CH2CH2CH2CH2CH= having a branched structure, -CH2CH2(CH-)CH2- having a branched structure, -CH2CH2CH2CH= having a branched structure. Z may not be a direct bond.

[0115] The monomer (a2) is CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -O-C(=O)-NH-R a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m-NH-C(=O)-O-R a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R a2 is preferably [where R 3 and X a2 are as defined above.]. Monomer (a2) is preferably CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 .

[0116] Monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of the long-chain alkyl isocyanate include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, behenyl isocyanate, and the like. Alternatively, monomer (a2) can also be produced by reacting a (meth)acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or long-chain alkyl alcohol. Examples of the long-chain alkylamine include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, behenylamine, and the like. Examples of the long-chain alkyl alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, and the like.

[0117] Preferred examples of monomer (2) are as follows. Stearyl (meth) acrylate, behenyl (meth) acrylate, stearyl α-chloroacrylate, behenyl α-chloroacrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, icosyl (meth) acrylate, icosyl α-chloroacrylate, stearic acid amidoethyl (meth) acrylate, 2-stearamidoethyl acrylate, CH2=CHC(=O)OC2H4NHSO2C 18 H 37 ; Stearyl (meth) acrylamide, behenyl (meth) acrylamide;

[0118] TIFF0007712587000003.tif2453

[0119] TIFF0007712587000004.tif2253 TIFF0007712587000005.tif2152 TIFF0007712587000006.tif2155

[0120] TIFF0007712587000007.tif2357 TIFF0007712587000008.tif2256 TIFF0007712587000009.tif2156

[0121] TIFF0007712587000010.tif2051 TIFF0007712587000011.tif2054 TIFF0007712587000012.tif2352 TIFF0007712587000013.tif2659

[0122] TIFF0007712587000014.tif2046

[0123] TIFF0007712587000015.tif2249 [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.] The compound of the above chemical formula is an acrylic compound with a hydrogen atom at the α-position. Specific examples may be a methacryl compound with a methyl group at the α-position and an α-chloroacrylic compound with a chlorine atom at the α-position.

[0124] Among the monomer (2), the amount of the 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 preferably 30% by weight or more.

[0125] The polymer of the present disclosure may further contain a repeating unit derived from one or more monomers selected from the following monomers (3) to (8).

[0126] (3) Monomer containing a hydrophilic group The polymer of the present disclosure may contain a monomer (3) containing a hydrophilic group. The monomer (3) is a monomer other than the monomer (1) and has a hydrophilic group. The hydrophilic group is preferably an oxyalkylene group (the alkylene group has 2 to 6 carbon atoms), and particularly preferably an oxyethylene group. In particular, the monomer (3) is preferably oxyalkylene (meth) acrylate, for example, polyalkylene (or monoalkylene) glycol mono (meth) acrylate and / or polyalkylene (or monoalkylene) glycol di (meth) acrylate, polyalkylene (or monoalkylene) glycol mono (meth) acrylamide.

[0127] The monomer (3) 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 are each independently an alkylene group having 2 to 6 carbon atoms, A b is a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH2=CX b C(=O)-, n is an integer from 1 to 90.] It is preferably an oxyalkylene (meth)acrylate represented by

[0128] Examples of the monomer (3) are of the formula: CH2=CX b C(=O)-O-(R b 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 are each independently a hydrogen atom or a methyl group, A bi are each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R b are each independently an alkylene group having 2 to 6 carbon atoms, n is an integer from 1 to 90 is.] It is preferably represented by

[0129] n may be, for example, from 1 to 50, particularly from 1 to 30, especially from 1 to 15 or from 2 to 15. Alternatively, n may be, for example, 1. R b may be a linear or branched alkylene group, for example, of the formula -(CH2) x - or -(CH2) x1 -(CH(CH3)) x2 -[wherein x1 and x2 are from 0 to 6, for example from 2 to 5, and the sum of x1 and x2 is from 1 to 6. -(CH2) x1 - and -(CH(CH3)) x2 - The order of - is not limited to the formula described and may be random. ] and may be a group represented by. -(R b O) n - In, R may be two or more (for example, 2 to 4, particularly 2), and -(R b O) n - is, for example, -(R 1 O) n1 - and -(R 2 O) n2 -[wherein R 1 and R 2 are different from each other and are alkylene groups having 2 to 6 carbon atoms, n1 and n2 are numbers of 1 or more, and the sum of n1 and n2 is from 2 to 90. ] and may be a combination of.

[0130] In formulas (b1), (b2) and (b3), R b is particularly preferably an ethylene group, a propylene group or a butylene group, particularly a butylene group. In formulas (b1), (b2) and (b3), R b may also be a combination of two or more alkylene groups. In that case, at least one of R is preferably an ethylene group, a propylene group or a butylene group. Combinations of R b include combinations of an ethylene group / propylene group, combinations of an ethylene group / butylene group, and combinations of a propylene group / butylene group. Monomer (3) may also be a mixture of two or more. In that case, at least one of monomer (3) is R in formula (b1), (b2) or (b3) bIt is preferably an ethylene group, a propylene group or a butylene group. When using the polyalkylene glycol di(meth)acrylate represented by the formula (b2), it is not preferable to use it alone as the monomer (3), and it is preferably used in combination with the monomer (b1). Also in that case, the compound represented by the formula (b2) is preferably limited to less than 30% by weight among the monomers (3) used.

[0131] Specific examples of the monomer (3) can be exemplified as follows, but are not limited thereto. CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)O-H CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H CH2=CHCOO-CH2CH2CH(CH3)O-H CH2=CHCOO-CH2CH(CH3)CH2O-H CH2=CHCOO-CH(CH3)CH2CH2O-H CH2=CHCOO-CH2CH(CH2CH3)O-H CH2=CHCOO-CH2C(CH3)2O-H CH2=CHCOO-CH(CH2CH3)CH2O-H CH2=CHCOO-C(CH3)2CH2O-H CH2=CHCOO-CH(CH3)CH(CH3)O-H CH2=CHCOO-C(CH3)(CH2CH3)O-H 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

[0132] 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

[0133] 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

[0134] 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

[0135] 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)O-H 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)O-H CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)O-H 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

[0136] 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

[0137] CH2=C(CH3)-C(=O)-NH-CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)O-H 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)O-H 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)O-H 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)O-H CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)O-H 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

[0138] 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

[0139] As the monomer (3), X 2 is preferably a hydrogen atom, and is preferably an acrylate or acrylamide. The monomer (3) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

[0140] (4) Monomer containing an ion-donating group The polymer of the present disclosure may contain a monomer (4) containing an ion-donating group. The monomer (4) is preferably a monomer containing an olefinic carbon-carbon double bond and an ion-donating group (particularly, an acrylic monomer). The ion-donating group is an anion-donating group and / or a cation-donating group.

[0141] Examples of the monomer having an anion-donating group include monomers having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Specific examples of the monomer having an anion-donating group include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, phosphoric acid (meth)acrylate, vinylbenzene sulfonic acid, acrylamide tertiary butyl sulfonic acid, etc., or salts thereof.

[0142] Examples of the salt of the anion-donating group include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salts, ethanolammonium salts, triethanolammonium salts, etc.

[0143] In the monomer having a cation-donating group, examples of the cation-donating group are amino groups, preferably tertiary amino groups and quaternary amino groups. In the tertiary amino group, the two groups bonded to the nitrogen atom are the same or different and are preferably an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (especially an aralkyl group, such as a benzyl group (C6H5-CH2-)). In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are preferably an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (especially an aralkyl group, such as a benzyl group (C6H5-CH2-)). In the tertiary amino group and the quaternary amino group, the remaining one group bonded to the nitrogen atom may have a carbon-carbon double bond. The cation-donating group may be in the form of a salt.

[0144] The cation-donating group which is a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, stearic acid, etc.) are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and their salts are preferred.

[0145] Specific examples of the monomer having a cation-donating group are as follows. CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (such as acetate) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (such as acetate) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (such as acetate) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (such as acetate) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (such as acetate) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (such as acetate) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br - CH2=C(CH3)COO-CH2CH2-N + (CH3)3I - CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3 CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0146] As the ion-donating group-containing monomer (4), methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate is preferable, and methacrylic acid or dimethylaminoethyl methacrylate is more preferable.

[0147] (5) Halogenated olefin monomer The polymer of the present disclosure may have a repeating unit derived from a halogenated olefin monomer (5). The halogenated olefin monomer (5) may not have a fluorine atom. The halogenated olefin monomer (5) is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin monomer (5) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin monomer (5) are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred because the water repellency (particularly the durability of the water repellency) is high. The presence of the repeating unit derived from the halogenated olefin monomer (5) increases the washing durability provided by the polymer of the present disclosure.

[0148] (6) Crosslinkable monomer The polymer of the present disclosure, the crosslinkable monomer has at least two reactive groups and / or ethylenically unsaturated double bonds (preferably, (meth) acrylate groups), and the crosslinkable monomer (6) may be a monomer that does not contain a fluorine atom. It may be a compound that does not contain a fluorine atom. The crosslinkable monomer (6) may be a compound having at least two ethylenically unsaturated double bonds (preferably, (meth) acrylate groups), or a compound having at least one ethylenically unsaturated double bond and at least one reactive group. Examples of the reactive group are a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, and the like.

[0149] The crosslinkable monomer may be a mono (meth) acrylate, di (meth) acrylate or di (meth) acrylamide having a reactive group.

[0150] One example of the crosslinkable monomer is a vinyl monomer having a reactive group.

[0151] Examples of the crosslinkable monomer include, but are not limited to, diacetone (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoxyacetoxyethyl (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, neopentyl glycol di(meth)acrylate, etc.

[0152] (7) Monomer containing a cyclic hydrocarbon group The polymer of this article may have a repeating unit derived from the monomer containing a cyclic hydrocarbon group (7). The monomer containing a cyclic hydrocarbon group (7) is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.

[0153] The monomer containing a cyclic hydrocarbon group (7) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0154] The cyclic hydrocarbon group may be alicyclic or aromatic, and is preferably alicyclic. The cyclic hydrocarbon group may be saturated or unsaturated, and is preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged cyclic group, and a bridged cyclic group is preferred. The cyclic hydrocarbon group may have a chain group (for example, a linear or branched hydrocarbon group).

[0155] The number of carbon atoms of 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.

[0156] Specific examples of the cyclic hydrocarbon group 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 groups which are substituents of these, and the like.

[0157] Specific examples of the cyclic hydrocarbon group-containing monomer 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, compounds obtained by substituting these acrylates with acrylamide, and the like. These may be used alone or in combination of two or more.

[0158] (8) Other monomers Other monomers are not limited to these examples and include acrylonitrile, organosiloxane-containing (meth)acrylate, short-chain alkyl (meth)acrylate, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, vinyl alkyl ether, and the like. Other monomers (8) may be used alone or in combination of two or more.

[0159] <Composition of the polymer> The combination of monomers (1) to (8) constituting the repeating unit of the polymer is not particularly limited as long as it contains (1), and is, for example, as follows (parentheses are omitted). (1) (1) + (2) (1) + (2) + (3) (1) + (3) (1) + (4) (1) + (2) + (3) + (4) (1) + (2) + (3) + (4) + (5) (1) + (2) + (3) + (4) + (5) + (6) (1) + (2) + (3) + (4) + (5) + (6) + (7) Furthermore, another monomer (8) may be used in combination with the above combinations. In the case of fiber products, it is preferable to use monomers (1) and (2) in combination.

[0160] [Amount of monomer (1)] The amount of the repeating unit derived from monomer (1) may be 0.1% by mass or more, 0.5% by mass or more, 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more based on the polymer. The amount of the repeating unit derived from monomer (1) 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, 50% by weight or less, 45% by weight or less, 35% by weight or less, 33% by weight or less, 30% by weight or less, 27% by weight or less, 25% by weight or less, 20% by weight or less, 17% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less based on the polymer.

[0161] The amount of the repeating unit derived from monomer (1) may be 100% by weight based on the polymer. That is, the polymer of the present disclosure may be a polymer of monomer (1). [Amount of hydrophobic monomer (2)]

[0162] The amount of the repeating unit derived from monomer (2) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more based on the polymer. The amount of the repeating unit derived from the monomer (2) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less based on the polymer. The amount of the repeating unit derived from the monomer (2) may be 0.01 part by weight or more, 0.1 part 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 with respect to 100 parts by weight of the repeating unit derived from the monomer (1). The amount of the repeating unit derived from the monomer (2) 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 with respect to 100 parts by weight of the repeating unit derived from the monomer (1). The weight ratio of the monomer unit (1) represented by the monomer unit (1) / monomer unit (2) in the polymer may be 0.001 or more, 0.005 or more, 0.010 or more, 0.020 or more, 0.040 or more, 0.080 or more, 0.1 or more, 0.2 or more, 0.4 or more, 0.8 or more, 1 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, 5.0 or more, or 10 or more. The weight ratio of the monomer unit (1) represented by the monomer unit (1) / monomer unit (2) in the polymer may be 30 or less, 20 or less, 10 or less, 5.0 or less, 3.0 or less, 2.5 or less, 2.0 or less, 1.5 or less, 1 or less, 0.8 or less, 0.4 or less, 0.2 or less, 0.1 or less, or 0.080 or less.

[0163] In one aspect, the amount of the repeating unit derived from the monomer (2) may be less than the amount of the repeating unit derived from the monomer (1).

[0164] [(3) Amount of the hydrophilic group-containing monomer] The amount of the repeating unit derived from the monomer (3) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more based on the polymer. The amount of the repeating unit derived from the monomer (3) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less based on the polymer. The amount of the repeating unit derived from the monomer (3) may be 0.01 part by weight or more, 0.1 part 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 with respect to 100 parts by weight of the repeating unit derived from the monomer (1). The amount of the repeating unit derived from the monomer (3) 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 with respect to 100 parts by weight of the repeating unit derived from the monomer (1).

[0165] [(4) Amount of the monomer containing an ion-donating group] The amount of the repeating unit derived from the monomer (4) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more based on the polymer. The amount of the repeating unit derived from the monomer (4) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less based on the polymer. The amount of the repeating unit derived from monomer (4) may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more with respect to 100 parts by weight of the repeating unit derived from monomer (1). The amount of the repeating unit derived from monomer (4) 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 with respect to 100 parts by weight of the repeating unit derived from monomer (1).

[0166] [(5) Amount of halogenated olefin monomer] The amount of the repeating unit derived from monomer (5) 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 with respect to the polymer. The amount of the repeating unit derived from monomer (5) 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 with respect to the polymer. The amount of the repeating unit derived from monomer (5) may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, 100 part by weight or more, 300 part by weight or more, 500 part by weight or more, 1000 part by weight or more with respect to 100 parts by weight of the repeating unit derived from monomer (1). The amount of the repeating unit derived from the monomer (5) 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 with respect to 100 parts by weight of the repeating unit derived from the monomer (1).

[0167] [(Amount of the crosslinkable monomer (6))] The amount of the repeating unit derived from the monomer (6) 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 with respect to the polymer. The amount of the repeating unit derived from the monomer (6) 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 with respect to the polymer. The amount of the repeating unit derived from the monomer (6) may be 0.01 part by weight or more, 0.1 part 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 with respect to 100 parts by weight of the repeating unit derived from the monomer (1). The amount of the repeating unit derived from the monomer (6) 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 with respect to 100 parts by weight of the repeating unit derived from the monomer (1).

[0168] [(Amount of the cyclic hydrocarbon group-containing monomer (7))] The amount of the repeating unit derived from the monomer (7) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more based on the polymer. The amount of the repeating unit derived from the monomer (7) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less based on the polymer. The amount of the repeating unit derived from the monomer (7) may be 0.01 part by weight or more, 0.1 part 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 with respect to 100 parts by weight of the repeating unit derived from the monomer (1). The amount of the repeating unit derived from the monomer (7) 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 with respect to 100 parts by weight of the repeating unit derived from the monomer (1).

[0169] [(8) Amount of other monomers] The amount of the repeating unit derived from the monomer (8) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more based on the polymer. The amount of the repeating unit derived from the monomer (8) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less based on the polymer. The amount of the repeating unit derived from the monomer (8) may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, 100 part by weight or more, 300 part by weight or more, 500 part by weight or more, or 1000 part by weight or more with respect to 100 parts by weight of the repeating unit derived from the monomer (1). The amount of the repeating unit derived from the monomer (8) 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 with respect to 100 parts by weight of the repeating unit derived from the monomer (1).

[0170] <Method for producing polymer> The polymers of the present disclosure can be produced by any of the usual polymerization methods, and the conditions of the polymerization reaction can also be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

[0171] In solution polymerization, in the presence of a polymerization initiator, the monomer is dissolved in an organic solvent, and after nitrogen substitution, it is heated and stirred at 30 to 120 °C for 30 minutes to 48 hours, for example, 3 to 24 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

[0172] The organic solvent is inert to the monomers and can dissolve them. For example, esters (e.g., esters having 2 to 30 carbon atoms, specifically ethyl acetate, butyl acetate), ketones (e.g., ketones having 2 to 30 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone), and alcohols (e.g., alcohols having 1 to 30 carbon atoms, specifically isopropyl alcohol) may be used. Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, 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, trichlorotrifluoroethane, and the like. The organic solvent is used in the range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total monomers.

[0173] In emulsion polymerization, a method is adopted in which monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, they are stirred and polymerized in the range of 50 to 80 °C for 30 minutes to 48 hours, for example, 3 to 24 hours. As the polymerization initiator, water-soluble ones such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine-dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, and oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the monomers.

[0174] In order to obtain a polymer aqueous dispersion with excellent storage stability, it is desirable to polymerize by micronizing monomers in water using an emulsifying device capable of imparting strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. Further, as the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and it is used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. It is preferable to use an anionic and / or nonionic and / or cationic emulsifier. When the monomers are not completely compatible, it is preferable to add a compatibilizer such as a water-soluble organic solvent or a low-molecular-weight monomer that can be sufficiently compatible with these monomers. By adding a compatibilizer, it is possible to improve the emulsifying property and copolymerizability.

[0175] Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc., and it may be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight with respect to 100 parts by weight of water. Examples of the low-molecular-weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and it may be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight with respect to 100 parts by weight of the total amount of the monomers.

[0176] In the polymerization, a chain transfer agent may be used. The molecular weight of the polymer can be changed according to the amount of the chain transfer agent used. Examples of the chain transfer agent include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, thioglycerol (especially, (for example, having 1 to 30 carbon atoms) alkyl mercaptan), and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of the 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 with respect to 100 parts by weight of the total amount of the monomers.

[0177] The polymer is preferably produced by an emulsion polymerization method or a solution polymerization method. After the polymer is produced by polymerization, it is preferable to add water (or an aqueous medium) to disperse the polymer in water. Water (or an aqueous medium) may be added after the polymer is produced by polymerization. For example, a monomer may be polymerized in the presence of an organic solvent to produce a polymer, and then water may be added to the polymer mixture to distill off the organic solvent to disperse the polymer in water. The organic solvent may not be distilled off. The surfactant may be added before or after polymerization, or may not be added. A good aqueous dispersion can be obtained even when the surfactant is not added.

[0178] <Composition> The composition of the present disclosure contains the polymer of the present disclosure. The composition of the present disclosure can be obtained by combining the polymer of the present disclosure with additional components (for example, an emulsifier, a liquid medium, a wax, etc.). The composition of the present disclosure can be obtained by polymerizing monomer (1) or monomer (1) and hydrophobic monomer (2) in the presence of additional components (for example, a surfactant, a liquid medium, a wax, etc.) of the present disclosure.

[0179] The composition can be made into an emulsion composition by containing the polymer of the present disclosure, an emulsifier, and water.

[0180] [Surfactant] The composition of the present disclosure may contain a surfactant as an additional component. In the composition, the surfactant may contain a nonionic surfactant. Further, the surfactant may contain one or more surfactants selected from a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant.

[0181] (Nonionic surfactant) Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.

[0182] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0183] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols having 1 to 6 (especially 2 to 5) hydroxyl groups and 1 to 50 (especially 10 to 30) carbon atoms (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50, especially 5 to 30 carbon atoms.

[0184] Examples of ester ethers are compounds obtained by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols having 1 to 6 (especially 2 to 5) hydroxyl groups and 1 to 50 (especially 3 to 30) carbon atoms (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50, especially 5 to 30 carbon atoms.

[0185] Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamine. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50, especially 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 1 to 3 amino groups and 1 to 5 hydroxyl groups and 2 to 50, especially 5 to 30 carbon atoms.

[0186] The polyhydric alcohol may be an alcohol having 2 to 5 hydroxyl groups and 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (e.g., having 5 to 50 carbon atoms).

[0187] The nonionic surfactant preferably is a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The alkylene group in the oxyalkylene group preferably has 2 to 10 carbon atoms. The number of oxyalkylene groups in the molecule of the nonionic surfactant generally preferably is 2 to 100. The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.

[0188] The nonionic surfactant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Further, the nonionic surfactant preferably has a structure that does not contain an aromatic group due to environmental problems (biodegradability, environmental hormones, etc.).

[0189] The nonionic surfactant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [wherein, R 1 is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group, each of R 2 is independently the same or different and is an alkylene group having 3 or more carbon atoms (for example, 3 to 10), R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, q is 0 or a number of 1 or more.] and may be a compound represented by.

[0190] R1 preferably has 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms. R 1 Preferred specific examples of R include a lauryl group, a tridecyl group, and an oleyl group. R 2 Examples of R include a propylene group and a butylene group. In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, a styrene chain, etc., and among them, an oxypropylene chain is preferable.

[0191] Specific examples of the nonionic surfactant include condensation products of ethylene oxide with hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 -C 18 ) amine, etc.

[0192] The proportion of the polyoxyethylene block can be 5 to 80% by weight, for example, 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer). The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic surfactant may be a mixture of a compound having an HLB (hydrophilic-lipophilic balance) of less than 15 (especially 5 or less) and a compound having an HLB of 15 or more. Examples of the compound having an HLB of less than 15 are sorbitan fatty acid esters. Examples of the compound having an HLB of 15 or more are polyoxyethylene alkyl ethers. The weight ratio of the compound having an HLB of less than 15 to the compound having an HLB of 15 or more may be from 90:10 to 20:80, for example, from 85:15 to 55:45. The nonionic surfactant may be a single kind or a mixture of two or more kinds.

[0193] (Cationic surfactant) The cationic surfactant is preferably a compound having no amide group.

[0194] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene-added type ammonium salt. Specific examples of the cationic surfactant include, but are not particularly limited to, amine salt type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc., quaternary ammonium salt type surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc.

[0195] Preferred examples of the cationic surfactant are R 21 -N + (-R 22 )(-R 23 )(-R 24 ) X - [In the formula, R 21 , R 22 , R 23 and R 24 are hydrocarbon groups having 1 to 40 carbon atoms, X is an anionic group.] compounds. R 21 , R 22 , R 23and -R 24 Specific examples of 24 are alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogen (e.g., chlorine), acid (e.g., hydrochloric acid, acetic acid). The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0196] The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula: R 1 p - N + R 2 q X - [wherein, R 1 is a linear and / or branched aliphatic (saturated and / or unsaturated) group having 12 or more carbon atoms (e.g., C 12 ~C 50 ), R 2 is H or an alkyl group having 1 to 4 carbon atoms, benzyl group, polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (especially 2, particularly 3) to 50) (CH3, C2H5 are particularly preferred), X is a halogen atom (e.g.,), fatty acid base having 1 to 4 carbon atoms, p is 1 or 2, q is 2 or 3, and p + q = 4.] and may be an ammonium salt represented by. The carbon number of R 1 may be 12 to 50, for example, 12 to 30.

[0197] Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0198] (Anionic surfactant) Examples of the anionic surfactant include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonated fatty acid salts, N-acyl amino acid type surfactants, phosphoric acid mono- or diester type surfactants, and sulfosuccinic acid esters.

[0199] (Amphoteric surfactant) Examples of the amphoteric surfactant include alanines, imidazolinium betaines, amide betaines, betaine acetates, etc. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminoacetic acid betaine, etc. are included.

[0200] The surfactant may be one or a combination of two or more of nonionic surfactants, cationic surfactants, and amphoteric surfactants.

[0201] (Amount of surfactant) The amount of the surfactant may be 0.1 part 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 with respect to 100 parts by weight of the polymer. The amount of the surfactant 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 with respect to 100 parts by weight of the polymer.

[0202] The surfactants exemplified in the present disclosure can also be used as emulsifiers. That is, the nonionic surfactant, cationic surfactant, anionic surfactant, and amphoteric surfactant exemplified in the present disclosure can be used as nonionic emulsifiers, cationic emulsifiers, anionic emulsifiers, and amphoteric emulsifiers.

[0203] [Liquid medium] The composition of the present disclosure may contain a liquid medium as an additional component. The liquid medium is water, an organic solvent, or a mixture of water and an organic solvent. Preferably, it is a mixture of water and an organic solvent.

[0204] Examples of the organic solvent are esters (for example, esters having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (for example, ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), alcohols (for example, alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (for example, toluene and xylene), petroleum solvents (for example, alkanes having 5 to 10 carbon atoms, specifically, naphtha, kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (for example, polyhydric alcohols such as alcohols, glycol solvents, ether forms of polyhydric alcohols (for example, monoether forms), etc.). These may be used alone or in combination of two or more.

[0205] (Amount of the liquid medium) The amount of the liquid medium may be 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, 90% by weight or more, 95% by weight or more, or 97% by weight or more based on the composition. The amount of the liquid medium may be 99.9% by weight or less, 99% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, or 50% by weight or less based on the composition.

[0206] The amount of the organic solvent may be 0.5% by weight or more, 1% by weight or more, 2% by weight or more, 3% by weight or more, 5% by weight or more, 7.5% by weight or more, 10% by weight or more, 12.5% by weight or more, 15% by weight or more, or 20% by weight or more based on the composition. The amount of the organic solvent may be 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less based on the composition.

[0207] The amount of the organic solvent may be 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 40% by weight or more based on the liquid medium. The amount of the organic solvent may be 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, 12.5% by weight or less, 7.5% by weight or less, or 5.0% by weight or less based on the liquid medium.

[0208] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more per 100 parts by weight of the polymer. The amount of the organic solvent may be 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 100 parts by weight of the polymer.

[0209] The amount of the organic solvent may be 0.5 parts by weight or more, 1 part by weight or more, 1.5 parts 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, 30 parts by weight or more, or 40 parts by weight or more with respect to 100 parts by weight of water. The amount of the organic solvent may be 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 25 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less with respect to 100 parts by weight of water.

[0210] [Silicone] The composition in the present disclosure may contain silicone, in addition to the monomer (1) and the hydrophobic monomer (2).

[0211] The silicone has the formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )2-O-] b -Si(R 53 )3(S1) [wherein each of R 51 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, each of R 53 independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a saturated hydrocarbon group having 1 to 40 carbon atoms, a represents an integer of 0 or more, b represents an integer of 1 or more, and (a + b) is 5 to 200.] It may be a polymer represented by.

[0212] R 51 and R 53 In, the alkyl group having 1 to 40 carbon atoms and the aryl group having 6 to 40 carbon atoms may be unsubstituted or may be substituted. R 51 and R 53Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group; a cyclopentyl group, a cyclohexyl group, a cycloheptyl group; a phenyl group, a tolyl group, a naphthyl group, or a group in which some or all of the hydrogen atoms bonded to these groups are substituted with a halogen atom, an amino group, a cyano group, etc. R 51 and R 53 are preferably a methyl group or an ethyl group. R 51 and R 53 In, the alkoxy group having 1 to 40 carbon atoms may be linear or branched. Examples of the alkoxy group having 1 to 40 carbon atoms are a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0213] Silicone may have at least one long-chain hydrocarbon group. For example, at least one of R 51 in the formula (S1), at least one of R 53 , or at least one of each of R 51 and R 53 may be a long-chain hydrocarbon group, and at least one (for example, one) of R 51 may be a long-chain hydrocarbon group. Here, the long-chain hydrocarbon group may be a saturated hydrocarbon group having 6 or more, 10 or more, 15 or more, or 20 or more, 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 the hydrocarbon group are a hexyl group (6 carbon atoms), an octyl group (8 carbon atoms), a lauryl group (12 carbon atoms), a myristyl group (14 carbon atoms), a stearyl group (18 carbon atoms), a behenyl group (22 carbon atoms), a tricosyl group (23 carbon atoms), a lignoceryl group (tetracosyl group, 24 carbon atoms), a cerotyl group (hexacosyl group, 26 carbon atoms), a montyl group (octacosyl group, 28 carbon atoms), a melissyl group (triacontane group, 30 carbon atoms), a dotriacontane group (32 carbon atoms).

[0214] In terms of being easy to manufacture industrially and being easily available, R which is a long-chain hydrocarbon group51 and R 53 R other than 51 and R 53 and R are preferably a hydrogen atom or a methyl group, more preferably a methyl group.

[0215] a is an integer of 0 or more. From the viewpoint of easy industrial production and easy availability, a may be 40 or less, 30 or less, 20 or less, and is preferably 30 or less.

[0216] The sum of a and b is 5 to 200. From the viewpoints of easy industrial production, easy availability, and easy handling, the sum of a and b is preferably 10 to 100, more preferably 40 to 60. a may be 0 to 150, for example, 1 to 100. The lower limit of b may be 1 or 2 or 3, and the upper limit of b may be 150, 10 or 5.

[0217] When a or b is 2 or more, R present in plural 51 and R 52 each of them may be the same or different.

[0218] R 51 and R 53 group (for example, when represented by the following formula (S2) R 51 and R 52 group and R 53 group), it is preferable that 50 mol% or more of the total is a methyl group.

[0219] The order of existence of the repeating units enclosed by a or b is not limited to the order of existence represented by the chemical formula and is arbitrary. That is, the silicone may be a random polymer or a block polymer.

[0220] For example, the silicone has the 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, each of R 51 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, and each of R 52 independently represents a long-chain hydrocarbon group, and each of R 53 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, and a represents an integer of 0 or more, b represents an integer of 1 or more, and (a + b) is 5 to 200.] It may be a polymer represented by In formula (S2), R 51 and R 53 may have an alkyl group having 3 to 40 carbon atoms or an unsaturated hydrocarbon group having 6 to 40 carbon atoms (for example, a hydrocarbon group having an aromatic ring), but it is preferable that they do not have these groups.

[0221] Examples of silicone are as follows. [Chemical formula] [In the formula, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a + b) is 5 to 200, and n is an integer of 1 to 36 (preferably n is a long-chain hydrocarbon group).]

[0222] Silicone can be synthesized by a conventionally known method. Silicone can be obtained, for example, by hydrosilylating an α-olefin with a silicone having an SiH group.

[0223] Examples of the silicone having an SiH group include methylhydrogen silicone having a polymerization degree of 10 to 200, or a copolymer of dimethylsiloxane and methylhydrogensiloxane. Among these, methylhydrogen silicone is preferable in terms of being easily manufacturable industrially and being easily available. The hydrogen silicone (for example, methylhydrogen silicone) is a polydiorganosiloxane in which a part of the side chain is substituted with hydrogen and the hydrogen atom is directly bonded to the silicon atom. In using the hydrogen silicone, a catalyst may be used to improve the reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine-based catalysts can be used. As these catalysts, metal organic acid salts are preferable, and as the organic acid, fatty acids are preferable. From the viewpoint of excellent handleability, zinc stearate or the like can be used. It is preferable to use the catalyst in an amount of 10 to 40% with respect to methylhydrogen silicone because the effect is easily exhibited. The amino-modified, epoxy-modified silicone, carboxy-modified silicone, and methylhydrogen silicone may be mixed in two or more kinds. All of them are silicones having a reactive group and are preferably silicones having film-forming properties. The film-forming property means that after each of the silicones is adhered to the fiber surface in an emulsion state, a solid film is formed instead of an oil-like or gel-like state.

[0224] α-Olefin is a compound that is a source of a long-chain hydrocarbon group in silicone. Specific examples of the α-olefin are 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triacontene, and 1-dotriacontene. The hydrosilylation reaction may be carried out by reacting the silicone having the SiH group with the α-olefin stepwise or at once in the presence of a catalyst as necessary.

[0225] The amounts of the silicone having the SiH group and the α-olefin used in the hydrosilylation reaction can be appropriately selected according to the SiH group equivalent, number average molecular weight, etc. of the silicone having the SiH group, respectively.

[0226] Examples of the catalyst used in the hydrosilylation reaction include compounds such as platinum and palladium, and among them, platinum compounds are preferred. Examples of the platinum compound include platinum(IV) chloride and the like.

[0227] The reaction conditions of 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. The hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of the inert gas include nitrogen, argon and the like. The reaction proceeds even without a solvent, but a solvent may also be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, butyl acetate and the like.

[0228] (Reactive silicone) The silicone may contain a reactive silicone. Examples of the reactive silicone include polysiloxanes having reactive groups at the side chain, one end, both ends, or the side chain and both ends. From the viewpoint of excellent anti-slip properties and excellent water repellency at the same time, it may be a polysiloxane having reactive groups at the side chain and / or both ends. The reactive silicone is not particularly limited as long as it has a reactive group in the molecule, and examples thereof include amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, hydrogen-modified silicone and the like. The reactive silicone may be one in which one or more substituents in the above formula (S1) or formula (S2) are replaced with reactive groups.

[0229] Examples of amino-modified silicones include those having a structure in which an amino group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. The alkylene group preferably has 2 or more carbon atoms. The divalent aromatic group preferably has 6 or more carbon atoms. The amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group. Examples of the organic group to which the amino group is bonded include the following: 2-aminoethyl group, N-methyl-2-aminoethyl group, N,N-dimethyl-2-aminoethyl group, N-ethyl-2-aminoethyl group, N,N-diethyl-2-aminoethyl group, N,N-methylethyl-2-aminoethyl group, 3-aminopropyl group, N-methyl-3-aminopropyl group, N,N-dimethyl-3-aminopropyl group, N-ethyl-3-aminopropyl group, N,N-diethyl-3-aminopropyl group, N,N-methylethyl-3-aminopropyl group. These functional groups may be in the side chain or at the terminal of the polysiloxane.

[0230] Examples of epoxy-modified silicones include those having a structure in which an epoxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Usually, it is bonded in the form of a glycidyl ether to the organic group. Examples of such functional groups include 3-glycidoxypropyl group and 2-glycidoxyethyl group. These functional groups may be in the side chain or at the terminal of the polysiloxane.

[0231] Examples of carboxy-modified silicones include those having a structure in which a carboxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. The alkylene group preferably has 2 or more carbon atoms. The divalent aromatic group preferably has 6 or more carbon atoms. Examples of such functional groups include 3-carboxypropyl group and 2-carboxyethyl group. These functional groups may be in the side chain or at the terminal of the polysiloxane.

[0232] (Silicone resin) The silicone may contain a silicone resin. The silicone resin is a silicone resin composed of at least one selected from R3SiO 1 / 2 units (M units), RSiO 3 / 2 units (T units), and SiO 4 / 2 units (Q units), where R is a linear or branched monovalent alkyl group having 1 to 18 carbon atoms, excluding silicone resins composed only of M units and only of Q units). From the viewpoint of exerting the effects of the present application, it is preferable that the silicone resin (3) does not contain R2SiO 2 / 2 units (D units).

[0233] 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. From the viewpoints of stability, availability of raw materials, and price when the silicone resin (3) is in a sol state, R is preferably a methyl group, and particularly preferably, 90% or more of all R is a methyl group. Note that different types of groups may be used in combination for R.

[0234] When the silicone resin contains R2SiO 2 / 2 units (D units), the low slipperiness of the composition may be impaired. Also, a silicone resin composed only of Q units may inhibit the water repellency of the composition.

[0235] Examples of the structure of the silicone resin include (i) silicone resins composed of M units and Q units, (ii) silicone resins composed of M units, T units, and Q units, (iii) silicone resins composed of M units and T units, (iv) silicone resins composed of T units and Q units, and (v) silicone resins composed only of T units. Preferably, they may be (i) silicone resins composed of M units and Q units and (v) silicone resins composed only of T units. For the silicone resin composed of (i) M units and Q units, the molar ratio (M / Q) of M units to Q units is preferably M / Q = 0.6 to 1.3, and more preferably M / Q = 0.8 to 1.1. Note that two or more of these silicone resins may be used in combination.

[0236] In addition, the silicone resin (3) can contain a structural unit containing a hydroxyl group bonded to a silicon atom. Specifically, (HO)RSiO 2 / 2 units, (HO)2RSiO 1 / 2 units, (HO)SiO 3 / 2 units, (HO)2SiO 2 / 2 units, (HO)3SiO 1 / 2 units may be mentioned, and a part of the hydroxyl group may be an alkoxy group represented by an RO group.

[0237] The sol containing the silicone resin can be obtained by a production method in which an organodisiloxane, a tetraalkoxysilane, and a partial hydrolysis condensate thereof are uniformly dispersed and polymerized in water containing a surfactant, as described in Patent 3852921, or by a production method in which the following silane compound is hydrolyzed in water.

[0238] A manufacturing method for hydrolyzing a silane compound in water will be described in detail. As a raw material for manufacturing, any silane compound can be used as long as the type of hydrolyzable group is chlorine or alkoxy, it contains one, three, or four hydrolyzable groups, and has an alkyl group satisfying the above conditions.Specifically, silane compounds that can be used include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrichlorosilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrichlorosilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, 2-ethylhexyltrichlorosilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, decyltriethoxysilane, cetyltrichlorosilane, cetyltrimethoxysilane, cetyltriethoxysilane, stearyltrichlorosilane, stearyltrimethoxysilane, stearyltriethoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, dimethylethylchlorosilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylpropylchlorosilane, dimethylpropylmethoxysilane, dimethylpropylethoxysilane, dimethylisopropylchlorosilane, dimethylisopropylmethoxysilane, dimethylisopropylethoxysilane, dimethylhexylchlorosilane, dimethylhexylmethoxysilane, dimethylhexylethoxysilane, dimethyldecylchlorosilane, dimethyldecylmethoxysilane, dimethyldecylethoxysilane, dimethylcetylchlorosilane, dimethylcetylmethoxysilane, dimethylcetylethoxysilane, dimethylstearylchlorosilane, dimethylstearylmethoxysilane, dimethylstearylethoxysilane, and partial hydrolyzates thereof. However, the silane compounds that can be used are not limited to these.From the viewpoints of operability, ease of removing by-products, and ease of obtaining raw materials, it is more preferable to use methoxysilane or ethoxysilane. One or a mixture of two or more of these silane compounds may be used.

[0239] As a method for hydrolyzing a silane compound in water, a generally known common method can be used. That is, a method of performing a hydrolysis reaction while dropping a silane compound into water, or a method of mixing water and a silane compound at once and then performing a hydrolysis reaction. When carrying out the hydrolysis reaction, a hydrolysis catalyst may be used. As the hydrolysis catalyst, a conventionally known catalyst can be used, and it is preferable to use an acidic or alkaline one. In the case of an acidic catalyst, hydrogen halide, carboxylic acid, sulfonic acid, acidic or weakly acidic inorganic salts, solid acids such as ion exchange resins are preferable. In the case of an alkaline catalyst, alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, alkali metal silanolates such as sodium silanolate and potassium silanolate, amines such as triethylamine, diethylamine, aniline, and aqueous ammonia can be used. It is preferable to adjust the addition amount so that the pH of the aqueous solution becomes 2 to 7 and 7 to 12. Further, after the reaction is completed, a neutralizing agent for neutralizing the acidic or alkaline catalyst may be added as necessary.

[0240] A surfactant may be added to the aqueous solution to disperse the silane compound and the hydrolysis reaction product in water. There is no particular limitation on the surfactant. For example, anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, and alkyl phosphates, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene oxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and polyoxyethylene fatty acid esters, cationic surfactants such as quaternary ammonium salts and alkylamine acetates, and amphoteric surfactants such as alkyl betaines and alkyl imidazolines can be used, and these can be used alone or in combination of two or more. Also, those showing acidity or alkalinity as the surfactant can also be used as the hydrolysis catalyst. There is no particular limitation on the addition amount when adding the surfactant, but it is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the silane compound. If it is less than 1 part by weight, the effect of adding the surfactant cannot be sufficiently obtained, and if it is more than 50 parts by weight, the water repellency of the water repellent may be impaired.

[0241] A hydrolysis catalyst and a surfactant may be added to the mixture of water and the silane compound as necessary, and the hydrolysis reaction may be carried out at 0 to 90 ° C for 10 minutes to 24 hours. Then, a silicone resin can be obtained by performing a neutralization reaction as necessary. Also, by-products such as alcohols and neutral salts produced by the hydrolysis reaction can be removed by distillation under reduced pressure or filtration. Various additives can be blended into this silicone resin. For example, a preservative, a thickener, etc. can be blended according to the purpose.

[0242] (Amount of silicone) The amount of silicone may be 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, or 20 part by weight or more with respect to 100 parts by weight of the polymer. The amount of silicone 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 with respect to 100 parts by weight of the polymer.

[0243] [Wax] The composition in the present disclosure preferably contains wax in addition to monomer (1) and hydrophobic monomer (2). By containing wax, good water repellency can be provided. The composition in the present disclosure may contain both silicone and wax, or may contain only one of silicone and wax.

[0244] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin waxes (such as polyethylene wax and polypropylene wax), oxidized polyolefin waxes, animal and plant waxes, and mineral waxes. Paraffin wax is preferred. Specific examples of the compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane), 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 of 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, 300 to 1000. These may be used alone or in combination of two or more.

[0245] The melting point of the wax may be 50°C or higher, 55°C or higher, 60°C or higher, 65°C or higher, or 70°C or higher, preferably 55°C or higher, more preferably 60°C or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0246] (Amount of wax) The amount of wax may be 0.1 part 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 based on 100 parts by weight of the polymer. The amount of wax 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 based on 100 parts by weight of the polymer.

[0247] [Organic acid] The composition of the present disclosure may contain an organic acid as an additional component. Known organic acids can be used. Preferred examples of the organic acid include carboxylic acids, sulfonic acids, sulfinic acids, etc., and carboxylic acids are particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., and formic acid or acetic acid is particularly preferred. In the present disclosure, one kind of organic acid may be used, or two or more kinds may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0248] (Amount of organic acid) The amount of organic acid may be 0.1 part 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 based on 100 parts by weight of the polymer. The amount of organic acid 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 based on 100 parts by weight of the polymer. The amount of organic acid may be adjusted so that the pH of the composition is 3 to 10, for example 5 to 9, particularly 6 to 8. The composition may be acidic (pH 7 or less, for example 6 or less).

[0249] [Hardening agent] The composition may contain a hardening agent (active hydrogen-reactive compound or active hydrogen-containing compound). After polymerization to obtain a polymer, a hardening agent may be added to the composition.

[0250] The curing agent (crosslinking agent) in the composition can cure the polymer well. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive group of the polymer. Examples of the active hydrogen-reactive compound are polyisocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0251] The curing agent may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of the polyisocyanate compound can include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates.

[0252] Examples of the aliphatic polyisocyanate are trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,03-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as 2,6-diisocyanatomethyl caproate, and lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane and other aliphatic triisocyanates. These may be used alone or in combination of two or more.

[0253] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates are 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0254] Examples of araliphatic polyisocyanates are araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates are 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0255] Examples of aromatic polyisocyanates are aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates are m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, etc. These may be used alone or in combination of two or more.

[0256] Derivatives of polyisocyanates include, for example, various derivatives such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretoimines, isocyanurates, iminooxadiazinediones, etc. of the above-mentioned polyisocyanate compounds. These may be used alone or in combination of two or more.

[0257] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound obtained by blocking the isocyanate groups of the polyisocyanate compound with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable even in an aqueous solution and can be used in the same aqueous solution as the composition.

[0258] The blocking agent blocks free isocyanate groups. The blocked polyisocyanate compound can regenerate isocyanate groups and easily react with hydroxyl groups, for example, by heating to 100 °C or higher, for example, 130 °C or higher. Examples of the blocking agent are phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, etc. The polyisocyanate compounds can be used alone or in combination of two or more.

[0259] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound are epoxy compounds having a polyoxyalkylene group, for example, polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether, etc. The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound are chloromethyl polystyrene, etc. The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound are (poly)acrylic acid, (poly)methacrylic acid, etc.

[0260] Specific examples of the ketone group-containing compound include (poly) diacetone acrylamide, diacetone alcohol, and the like. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide, and the like. Specific examples of the melamine compound include melamine resin, methyl etherified melamine resin, and the like.

[0261] (Amount of curing agent) The amount of the curing agent may be 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, or 20 part by weight or more with respect to 100 parts by weight of the polymer. The amount of the curing agent is 50 parts by weight or less, 40 parts by weight or more with respect to 100 parts by weight of the polymer.

[0262] [Hydrophilic particles] The composition in the present disclosure may contain hydrophilic particles as an additional component. Here, hydrophilicity means the property that the particles are easily dispersed in an aqueous solvent without aggregating. For example, when 1.0% by weight of particle powder and an arbitrary dispersant are added to an aqueous solvent and stirred at 700 rpm for 10 minutes using a homomixer and then left to stand for 1 hour, if precipitation or aggregation of the particles cannot be visually confirmed, it is considered to have hydrophilicity. Also, for commercially available particle aqueous dispersions in a state where the particles are dispersed in an aqueous solvent, the contained particles are considered to have hydrophilicity.

[0263] The hydrophilic particles may have a hydrophilic group on the surface. Examples of the hydrophilic group include a cationic group, an anionic group, an amino group, a hydroxyl group, and the like. The surface of the hydrophilic particles may be subjected to a hydrophilization treatment, but generally, a hydrophobization treatment is not performed.

[0264] The hydrophilic particles are not particularly limited as long as they have hydrophilicity, and examples include inorganic particles such as alumina, silica, and titania (e.g., inorganic oxide particles), and organic particles such as latex, acrylic, and nylon. Among these, inorganic particles are preferred because of their easy handling properties, etc., and at least one selected from the group consisting of silica and alumina is particularly preferred. As commercially available products, examples of silicon oxide particles include "Snowtex ST-OYL", "Snowtex ST-AK-L", and "Snowtex ST-AK-YL" (manufactured by Nissan Chemical Industries, Ltd.); examples of titanium oxide particles include "TA300" and "TA300D" (manufactured by Fuji Titanium Industry Co., Ltd.); and examples of aluminum oxide particles include "TM-5D" (manufactured by Dainippon Chemical Industry Co., Ltd.). These may be used alone or in combination of two or more.

[0265] (Average primary particle size) The average primary particle size of the hydrophilic particles may be 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, or 30 nm or more. The average primary particle size of the hydrophilic particles may be 600 nm or less, 400 nm or less, 200 nm or less, 100 nm or less, 40 nm or less, 37.5 nm or less, 35 nm or less, 32.5 nm or less, 30 nm or less, 27.5 nm or less, 25 nm or less, or 22.5 nm or less, and preferably 40 nm or less. By being within the above range, good water repellency can be provided. The average primary particle size can be measured with a microscope (scanning electron microscope or transmission electron microscope). Specifically, an arbitrary position on the fabric is observed from above at an arbitrary magnification with a microscope. Next, when the particle shape is spherical, its diameter, and when it is non-spherical, the average value of the longest diameter and the shortest diameter are regarded as the particle size (grain size). The grain sizes of all the particles present in the field of view are measured, and the process of moving the field of view and measuring the grain size again is repeated to measure the grain size at 10 points or more, and the average value is taken as the average primary particle size.

[0266] (Turbidity) The turbidity of an aqueous dispersion prepared by dispersing hydrophilic particles in water at a concentration of 10 g / l and adjusting the pH to 7 may be 0.1 ppm or more, 1 ppm or more, 5 ppm or more, or 10 ppm or more. The turbidity of an aqueous dispersion prepared by dispersing hydrophilic particles in water at a concentration of 10 g / l and adjusting the pH to 7 may be 200 ppm or less, 100 ppm or less, 50 ppm or less, 20 ppm or less, 10 ppm or less, 5 ppm or less, or 2.5 ppm or less, and is preferably 20 ppm or less. By being in the above range, water repellency, slip resistance, and storage stability can be satisfactorily combined. The turbidity can be calculated based on a calibration curve (0 to 1000 ppm range) prepared with the turbidity of kaolin (pigment) as a standard sample based on JIS K0101, drinking water test method, using an integrating sphere turbidimeter PT200 manufactured by Nitto Seiko Analytech Co., Ltd.

[0267] (Zeta potential) The zeta potential of an aqueous dispersion prepared by dispersing hydrophilic particles in water at a concentration of 10 g / l and adjusting the pH to 7 may be -20 mV or more, -10 mV or more, 0 mV or more, +5 mV or more, +10 mV or more, or +20 mV or more, preferably 0 mV or more, or +10 mV or more. The zeta potential of an aqueous dispersion prepared by dispersing hydrophilic particles in water at a concentration of 10 g / l and adjusting the pH to 7 may be +200 mV or less, +150 mV or less, +100 mV or less, +50 mV or less, +30 mV or less, +100 mV or less, +10 mV or less, or +5 mV or less, preferably +100 mV or less. By having the turbidity in the above range, the water repellency, slip resistance, and storage stability can be well combined. The zeta potential can be measured, for example, using a commercially available zeta potential measuring device.

[0268] (Amount of hydrophilic particles) The amount of the hydrophilic particles may be 0.01% by weight or more, 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 1% by weight or more, 2% by weight or more, 3% by weight or more, or 5% by weight or more, preferably 0.5% by weight or more, particularly preferably 2% by weight or more, based on the total of the polymer and the hydrophilic particles. The amount of the hydrophilic particles may be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 3% by weight or less, or 2% by weight or less, preferably 12% by weight or less, based on the total of the polymer and the hydrophilic particles. When the amount of the hydrophilic particles is within the above range, water repellency can be provided well.

[0269] The silicone, wax, hydrophilic particles, liquid medium, dispersant, surfactant, or curing agent listed above may be added after the polymer is produced, or the monomer of the polymer may be polymerized in the presence of the silicone, wax, hydrophilic particles, liquid medium, dispersant, surfactant, or curing agent listed above to produce the polymer.

[0270] [Other components] The composition may contain other components in addition to the above components. After producing the polymer, other components may be added. Examples of other components include water and / or oil repellents, slip inhibitors, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above components, as other components, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying rate adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage preventers, anti-wrinkle agents for washing, shape retainers, drape retention agents, ironing property improvers, brightening agents, whitening agents, fabric softening clay, migration inhibitors such as polyvinylpyrrolidone, polymer dispersants, soil release agents, scum dispersants, fluorescent brightening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, defoaming agents, silk powder, surface modified products thereof, and emulsion dispersions that can impart silk texture and functions such as water absorption and release properties, specifically K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (Jomo), Silkgen G Soluble S (Ichimaru Pharcos), nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units, for example, contamination preventers such as FR627 manufactured by Gohou Chemical Industry Co., Ltd., SRC-1 manufactured by Clariant Japan Co., Ltd., etc. These may be used alone or in combination of two or more.

[0271] (Antistatic agent) Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, 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; nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives, etc. These may also be ionic conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic, and zwitterionic ionic conductive groups. These may be used alone or in combination of two or more.

[0272] (Preservative) Preservatives can be mainly used to enhance the antiseptic power and bactericidal power and maintain the preservability during long-term storage. Examples of preservatives include isothiazolone-based organosulfur compounds, benzisothiazolone-based organosulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, etc. The amount of the preservative is preferably 0.0001 to 1% by weight based on the total weight of the composition. When the amount of the preservative is not less than the lower limit value of the above range, the addition effect of the preservative can be sufficiently obtained, and when it is not more than the upper limit value, the storage stability of the composition is good.

[0273] (UV absorber) UV absorbers are agents having the effect of protecting against ultraviolet rays and are components that absorb ultraviolet rays and convert them into and emit infrared rays, visible light, etc. Examples of UV absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole-based compounds, 4-t-butyl-4'-methoxybenzoylmethane, etc.

[0274] (Antibacterial agent) Antibacterial agents are components that have the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors resulting from the decomposition products of microorganisms. Examples of antibacterial agents include cationic bactericides such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, polylysine, etc.

[0275] (Deodorant) Examples of deodorants include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (zinc complex of trisodium methylglycinediacetate described in WO 2012 / 090580).

[0276] (fragrance) The fragrance is not particularly limited, and lists of usable fragrance raw materials can be found in various documents, such as "Perfume and Flavor Chemicals", Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994); "Synthetic Fragrances: Chemistry and Product Knowledge", Indo Genichi, Kagaku Kogyo Nipposha (1996); "Perfume and Flavor Materials of Natural Origin", Steffen Arctander, Allured Pub. Co. (1994); "Encyclopedia of Fragrance", edited by the Japan Fragrance Manufacturers Association, Asakura Shoten (1989); "Perfumery Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996); and "Flower oils and Floral Compounds In Perfumery", Danute Lajaujis Anonis, Allured Pub. Co. (1993), each of which is incorporated herein by reference.

[0277] (Amount of other ingredients) The amount of the other component may be 0.1 part 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 with respect to 100 parts by weight of the polymer. The amount of the other component 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 with respect to 100 parts by weight of the polymer.

[0278] (Amount of polymer) The amount of the polymer may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more in the composition. The amount of the polymer may be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less in the composition.

[0279] (Use of the composition) Examples of the use of the composition in the present disclosure include use as an external treatment agent (surface treatment agent) or an internal treatment agent, a repellent (such as a water repellent, an oil repellent, or a water and oil repellent, particularly a water repellent), an antifouling agent, a soil release agent, a release agent, a mold release agent (an external mold release agent or an internal mold release agent), etc. Alternatively, the composition in the present disclosure can be used as an external treatment agent (surface treatment agent) or an internal treatment agent, a repellent (such as a water repellent, an oil repellent, or a water and oil repellent, particularly a water repellent), an antifouling agent, a soil release agent, a release agent, a mold release agent (an external mold release agent or an internal mold release agent).

[0280] (Method for producing the composition) The method for producing the composition may include a step of reacting (polymerizing) monomer (1) in a medium (such as a liquid medium) containing monomer (1) and the additional components (such as an emulsifier, a liquid medium, a wax, etc.) mentioned above to obtain a polymer. Alternatively, the method for producing the composition may include a step of adding additional components (such as an emulsifier, a liquid medium, a wax, etc.) to a solution or dispersion of the polymer, or a step of mixing a solution or dispersion of the polymer and a solution or dispersion of the additional components (such as an emulsifier, a liquid medium, a wax, etc.).

[0281] In order for the composition to exhibit high water repellency, it is preferable to subject the composition to ultrasonic waves (ultrasonic treatment). It is preferable to perform the ultrasonic treatment immediately before application to the object to be treated. For example, the composition is applied to the object to be treated 1 minute to 1 hour after the ultrasonic treatment. The ultrasonic treatment can be performed by applying ultrasonic waves to the composition. There are no particular restrictions on the ultrasonic generator, but an output of 500 W or more, for example, 500 to 2000 W, is preferable in terms of efficient mixing. The treatment time of the ultrasonic treatment may be 0.5 minutes to 60 minutes. For example, treatment with a 500 W ultrasonic generator for 10 minutes results in a uniform composition.

[0282] Examples of the polymerization method include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0283] In solution polymerization, in the presence of a polymerization initiator, the monomer is dissolved in an organic solvent, and after nitrogen substitution, a method of heating and stirring at 30 to 120 °C for 1 to 10 hours is adopted. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, etc. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, based on 100 parts by weight of the monomer.

[0284] The organic solvent is inert to the monomers and dissolves them. For example, it may be an ester (e.g., an ester having 2 to 40 carbon atoms, specifically ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically ethanol, butanol, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like. The organic solvent is used in the range of 10 to 3000 parts by weight, for example, 50 to 2000 parts by weight, based on 100 parts by weight of the total monomers.

[0285] In emulsion polymerization, a method is adopted in which the monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, the mixture is stirred and polymerized at 50 to 80 °C for 1 to 20 hours. As the polymerization initiator, 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, ammonium persulfate, and oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the monomers.

[0286] In order to obtain a polymer aqueous dispersion with excellent storage stability, it is desirable to polymerize by micronizing monomers in water using an emulsifying device capable of imparting strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and they are used in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the monomers. It is preferable to use an anionic and / or nonionic and / or cationic emulsifier. When the monomers are not completely compatible, it is preferable to add a compatibilizer such as a water-soluble organic solvent or a low-molecular-weight monomer that can be sufficiently compatible with these monomers. By adding a compatibilizer, it is possible to improve the emulsifying property and copolymerizability.

[0287] As the water-soluble organic solvent, the above-mentioned organic solvents 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 mentioned, and they may be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight based on 100 parts by weight of water. As the low-molecular-weight monomers, methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc. may be mentioned, and they may be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight based on 100 parts by weight of the total amount of the monomers.

[0288] In the polymerization, a chain transfer agent may be used. The molecular weight of the polymer can be changed according to the amount of the chain transfer agent used. Examples of the chain transfer agent are mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, thioglycerol (especially alkyl mercaptans (for example, having 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of the 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 based on 100 parts by weight of the total amount of the monomers.

[0289] The composition may be in the form of a solution, an emulsion (especially an aqueous dispersion), or an aerosol.

[0290] <Water repellent agent> The water repellent agent of the present disclosure contains the polymer of the present disclosure. The water repellent agent of the present disclosure may be the composition of the present disclosure. That is, the composition of the present disclosure can be used as the water repellent agent as it is. The water repellent agent of the present disclosure may be prepared by applying various materials and conditions used for preparing the composition of the present disclosure in addition to the polymer of the present disclosure.

[0291] The water repellent agent in the present disclosure may not have any selected from the group consisting of a compound having a fluoroalkyl group with 8 or more carbon atoms, a compound having a perfluoroalkyl group with 8 or more carbon atoms, a compound having a fluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The water repellent agent in the present disclosure can impart liquid repellency to the substrate even without containing these fluorine compounds.

[0292] <Uses of the water repellent agent> Examples of the uses of the water repellent agent in the present disclosure include an external treatment agent (surface treatment agent) or an internal treatment agent, a repellent agent (such as a water repellent agent, an oil repellent agent, or a water and oil repellent agent, particularly a water repellent agent), an antifouling agent, a soil release agent, a release agent, a mold release agent (an external mold release agent or an internal mold release agent), and the like.

[0293] <Manufacturing method of the water repellent agent> Regarding the manufacturing method of the water repellent agent of the present disclosure, the manufacturing method of the composition of the present disclosure is incorporated.

[0294] <Manufacturing method of the treated product> The manufacturing method of the treated product in the present disclosure includes a step of applying the water repellent agent of the present disclosure to a substrate.

[0295] [Treated product] Examples of substrates treated with the water repellent of the present disclosure include fiber substrates, stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster, etc. Various examples can be given as fiber products. For example, animal and plant natural 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 mixed fibers thereof can be mentioned. As an example of the substrate treated with the water repellent, the example of woven and knitted fabrics will be described in detail.

[0296] (Woven and knitted fabrics) · Manufacturing method of woven and knitted fabrics Woven and knitted fabrics can be obtained by weaving and knitting long fibers and short fiber yarns made of the above fibers to obtain a green fabric, and then subjecting this to post-processing and water repellent treatment. Weaving and knitting can be carried out using known weaving machines and knitting machines, and known equipment can also be used for the preparatory processes prior to weaving and knitting.

[0297] The woven and knitted fabrics after weaving and knitting can be post-processed using known scouring and dyeing methods and equipment adapted to the fiber materials of the woven and knitted fabrics.

[0298] After post-processing, the woven and knitted fabrics can be subjected to water repellent treatment. In the water repellent treatment, first, an aqueous solution containing a water repellent (which may be the water repellent or composition in the present disclosure) is prepared. Next, based on methods such as padding, spraying, kiss roll coater method, slit coater method, etc., the above aqueous solution is applied to the woven and knitted fabrics after the above post-processing, and after drying, heat treatment can be carried out. The above aqueous solution may also contain a crosslinking agent, softening agent, antistatic agent, etc. as required. After the water repellent treatment, the woven and knitted fabrics may be calendered for further improvement of the water repellent performance.

[0299] The knitted or woven fabric is suitably used for clothing applications that require water repellency, particularly for sports wear applications such as outdoor, skiing, snowboarding, golf, etc., and for uniform wear applications.

[0300] · Laminated fabric It may be provided as a laminated fabric having a moisture permeable and waterproof layer provided on one side of the knitted or woven fabric of the present disclosure. The moisture permeable and waterproof layer may be directly laminated to the knitted or woven fabric, or may be laminated to the knitted or woven fabric via an adhesive layer. When using the laminated fabric of the present disclosure for clothing applications, etc., the knitted or woven fabric side is disposed on the side that repels rainwater, etc.

[0301] · Moisture permeable and waterproof layer The moisture permeable and waterproof layer is a layer that covers one surface of the knitted or woven fabric, and is a layer formed of a resin or a structured film having waterproofness and moisture permeability.

[0302] The moisture permeable and waterproof layer may be formed by directly applying a resin (the resin constituting the moisture permeable and waterproof layer) to the knitted or woven fabric, or may be laminated on one side of the knitted or woven fabric via an adhesive layer described later.

[0303] The resin constituting the moisture permeable and waterproof layer is not particularly limited, but non-porous and porous-forming resins are used. For non-porous ones, polyurethane resins and polyester elastomer resins having hydrophilic components are used because they have moisture permeability. Also, for porous ones, in addition to polyurethane resins that form wet porous membranes and polyurethane resins that are made porous by electrospinning, PTFE porous membranes and porous membranes of PE and PP are also used.

[0304] As the polyurethane resin, a conventionally known one obtained by reacting a polyisocyanate component and a polyol component can be adopted.

[0305] A moisture-permeable and waterproof film having a microporous structure can be obtained by a wet coagulation method using a DMF solution of a polyurethane resin containing inorganic fine powder. Examples of the inorganic fine powder include fine powder composed of silicon dioxide, aluminum oxide, titanium dioxide, or the like. Further, the average primary particle diameter of the inorganic fine powder is preferably about 7 to 40 nm. The amount of the inorganic fine powder is preferably 3 to 50% by weight, more preferably 5 to 50% by weight, based on the total amount of the moisture-permeable and waterproof layer.

[0306] The thickness of the moisture-permeable and waterproof layer is preferably 5 μm or more, more preferably 10 to 30 μm. When the thickness is within the above range, the balance between waterproofness and moisture permeability is excellent, and there are further advantages in terms of texture.

[0307] ·Adhesive layer The laminated fabric preferably includes an adhesive layer. That is, the woven or knitted fabric and the moisture-permeable and waterproof layer are preferably laminated via an adhesive layer. Further, the adhesive layer is preferably a discontinuous layer such as dots or a lattice in terms of moisture permeability.

[0308] The type of the adhesive constituting the adhesive layer is not particularly limited, but it is preferably excellent in compatibility with the moisture-permeable and waterproof layer. For example, when a resin mainly composed of a polyurethane resin is selected as the resin constituting the moisture-permeable and waterproof layer, it is preferable to employ an adhesive layer composed of a polyurethane-based adhesive. The polyurethane-based adhesive may be of any structure such as an ether-based, ester-based, or polycarbonate-based structure.

[0309] The adhesive layer may be formed on the entire surface of one side of the woven or knitted fabric, or may be formed in a pattern from the viewpoints of moisture permeability or texture. The pattern form is not particularly limited, and examples include dot-like, linear, lattice-like, checkered pattern, and tortoise shell pattern, and it is preferable that any of them is uniformly arranged throughout.

[0310] The thickness of the adhesive layer is preferably about 10 to 100 μm, more preferably 20 to 80 μm.

[0311] · Lining fiber fabric In the laminated fabric of the present disclosure, a lining fiber fabric may be laminated on the moisture permeable waterproof layer (the side opposite to the surface on which the knitted or woven fabric of the present disclosure is laminated in the moisture permeable waterproof layer). The lining fiber fabric can protect the moisture permeable waterproof layer and can be made to be more excellent in waterproof property (water pressure resistance) and strength.

[0312] Examples of the lining fiber fabric include various woven fabrics, knitted fabrics, etc. Among them, knitted fabrics are more suitable because the constituent yarns are more likely to protrude on the surface compared to woven fabrics and do not have a flat surface state, and the anchor effect is more exerted and it is difficult to peel off from the moisture permeable waterproof layer. Also, tricot knitted fabric is preferable in that it can obtain a long live yarn during knitting and has few joints, and can be uniformly laminated on the moisture permeable waterproof layer.

[0313] The material of the fiber constituting the lining fiber fabric is not particularly limited and can be appropriately selected, but nylon fiber is preferably used. This is because generally acidic dyes are used in nylon fibers, so migration sublimation of disperse dyes to the moisture permeable waterproof layer, which is a problem in polyester fibers and the like where disperse dyes are used, hardly occurs. The form (long fiber, short fiber or spun yarn) or fineness of the constituent fibers of the lining fiber fabric is not particularly limited and can be appropriately selected within a range that does not impair the effects of the present disclosure.

[0314] · Characteristics of laminated fabric The laminated fabric has excellent waterproof property. Suitable examples of the waterproof property of the laminated fabric of the present disclosure include that the water level measured according to the water resistance test defined in JIS L 1092:2009 A method (low water pressure method) is, for example, 10000 mm or more, preferably 15000 mm or more, more preferably 16000 mm or more, and particularly preferably 20000 mm or more.

[0315] The laminated fabric has excellent moisture permeability. Suitable examples of the moisture permeability of the laminated fabric of the present disclosure include that the moisture permeability measured according to JIS L 1099:2021 B-1 method (potassium acetate method) is, for example, 10000 g / m 2· Above 24 hours, preferably 15000 g / m 2 · Above 24 hours, more preferably 20000 g / m 2 · Above 24 hours can be mentioned. Regarding the upper limit value of the moisture permeability, there is no particular limitation. For example, 40000 g / m 2 · 24 hours or 35000 g / m 2 · 24 h·mm can be mentioned. Also, the moisture permeability measured according to JIS L 1099:2021 A-1 method (calcium chloride method) is, for example, 4000 g / m 2 · Above 24 hours, preferably 8000 g / m 2 · Above 24 hours, more preferably 10000 g / m 2 · Above 24 hours can be mentioned. Regarding the upper limit value of the moisture permeability, as the limit of the measurement method, it is 13000 - 15000 g / m 2 · It is about 24 hours.

[0316] In the laminated fabric of the present disclosure, as the peel strength between the woven or knitted fabric and the moisture permeable and waterproof layer, the peel strength measured according to the method of JIS K 6404-2 is, for example, preferably 2.55 N / 2.54 cm or more for clothing applications, and may preferably be 5 N / 2.54 cm or more in the intended use.

[0317] · Manufacturing method of the laminated fabric The manufacturing method of the laminated fabric is not particularly limited. For example, the first manufacturing method and the second manufacturing method shown below can be mentioned. First manufacturing method: A step of forming the moisture permeable and waterproof layer by applying the resin constituting the moisture permeable and waterproof layer on the surface of the woven or knitted fabric is included. Second manufacturing method: A step of forming an adhesive layer on the woven or knitted fabric or the moisture permeable and waterproof layer, and a step of bonding the woven or knitted fabric and the moisture permeable and waterproof layer through the adhesive layer are included.

[0318] In the first manufacturing method, as a method of applying a resin that forms a moisture-permeable and waterproof layer on the surface of a knitted or woven fabric, for example, a coating method can be mentioned. In the coating method, a knife coater or a comma coater can be used. Also, from the viewpoint of providing excellent moisture permeability, it is preferable to obtain the moisture-permeable and waterproof layer by a wet method.

[0319] In the second manufacturing method, as a method of forming an adhesive layer on a knitted or woven fabric or a moisture-permeable and waterproof layer, for example, a lamination method can be mentioned. In the lamination method, a method using a resin solution or a method using hot melt can be adopted for forming the adhesive layer. First, a resin composition for forming a moisture-permeable and waterproof layer (for example, a resin composition containing a resin and an organic solvent) is provided with a clearance on the surface of a release material (release paper, release cloth, release film, etc.), and the moisture-permeable and waterproof layer is formed while adjusting the thickness, and then dried and heat-treated to completely react to obtain a film. The release material can be appropriately removed after laminating or aging. Also, when laminating by a hot melt method, the release material can be peeled off and the film can be laminated alone. Also, the moisture-permeable waterproof film can be laminated with a film formed by an extrusion method such as a T-die method or inflation without a solvent, a porous film formed by an electrospinning method, a porous film such as PTFE, PE, or PP.

[0320] Then, an adhesive layer is formed on the knitted or woven fabric or the moisture-permeable and waterproof layer. For example, in the case of a method using a resin solution, a two-component curable polyurethane resin solution adjusted to a viscosity in the range of 500 to 5000 mPa·s can be applied entirely or in a pattern. Then, it is dried to form an adhesive layer, and the knitted or woven fabric and the moisture-permeable and waterproof layer are laminated through the adhesive layer, and both are crimped or thermocompression bonded to execute the second manufacturing method.

[0321] On the one hand, in the case of hot melt, it is preferable to use a moisture-curing resin that reacts with moisture in the air, and in practical use, those that melt in a temperature range of about 80 to 150 °C are more preferable. In this case, first, the hot melt resin is melted while considering the melting point of the resin, the viscosity during melting, etc. Then, the melted resin is applied onto the woven or knitted fabric or the moisture-permeable waterproof layer and aged while cooling at room temperature to form an adhesive layer. Then, the woven or knitted fabric and the moisture-permeable waterproof layer are bonded together through the adhesive layer and crimped, whereby the second manufacturing method can be carried out. Alternatively, when emphasizing the texture, it can also be applied to the moisture-permeable waterproof film in a pattern and bonded to the woven or knitted fabric.

[0322] Thereafter, a lining fiber fabric can be laminated onto the moisture-permeable waterproof layer using a known appropriate method.

[0323] · Applications of the laminated fabric The laminated fabric is excellent in water repellency and moisture-permeable waterproofness, and the moisture-permeable waterproof layer does not peel off even in a harsh environment, so it is preferably used in fields such as uniform clothing, sports clothing, and outdoor products used outdoors.

[0324] [Processing method] The water repellent of the present disclosure can be applied to a substrate (especially a fiber substrate) by a conventionally known method as a treating agent (especially a surface treating agent). The water repellent in the present disclosure may be dispersed and diluted in an organic solvent or water if necessary, and adhered to the surface of the substrate and dried by a known method such as dip coating, spray coating, foam coating, etc. After drying, a fiber product with the solid component in the water repellent adhered thereto is obtained. Further, if necessary, it may be applied together with a suitable crosslinking agent and cured. Furthermore, it is also possible to use in combination the water repellent of the present disclosure and various additives such as a water and / or oil repellent, an anti-slip agent, an antistatic agent, a hand modifier, a softening agent, an antibacterial agent, a flame retardant, a paint fixing agent, an anti-wrinkle agent, a drying rate regulator, a crosslinking agent, a film-forming aid, a compatibilizer, an antifreezing agent, a viscosity regulator, an ultraviolet absorber, an antioxidant, a pH regulator, an insect repellent, an antifoaming agent, etc. Examples of the various additives may be the same as those described as "other components" in the above composition. The concentration of the polymer in the treating agent brought into contact with the substrate may be appropriately changed depending on the use, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0325] [Fiber product] Although various examples can be given as the fiber substrate which is the substrate, for example, cloth products and paper products can be mentioned. The fiber product which is the substrate is also referred to as a fiber substrate.

[0326] Examples of cloth products include animal and plant natural 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 fiber, carbon fiber, and asbestos fiber, or mixed fibers thereof. Cloth products include woven fabrics, knitted fabrics, and non-woven fabrics, cloth in the form of clothing, and carpets, but the fibers, yarns, and intermediate fiber products (for example, sliver or roving, etc.) in the state before being made into cloth may be treated.

[0327] Examples of paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, bleached or unbleached high-yield pulp such as mechanical pulp or thermomechanical pulp, waste paper pulp such as newspaper waste paper, magazine waste paper, cardboard waste paper or deinked waste paper, etc., containers made of paper, and molded bodies made of paper, etc. Specific examples of paper products include packaging paper for food, base paper for gypsum board, base paper for coating, medium paper, general liner and core, neutral pure white roll paper, neutral liner, rust-proof liner and metal laminated paper, kraft paper, neutral printing and writing paper, neutral base paper for coating, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, mold paper (mold container), etc.

[0328] The water repellent can be applied to the fiber substrate by any of the methods known for treating a fiber substrate (e.g., cloth) with a liquid. The fiber substrate may be immersed in the water repellent, or a solution may be adhered or sprayed onto the fiber substrate. The treated fiber substrate is preferably dried and cured by heating in order to exhibit water repellency. The heating temperature may be, for example, 80°C to 250°C, 100°C to 170°C or 100°C to 120°C. The heating temperature may preferably be 100°C to 170°C. In the present disclosure, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0329] Alternatively, the water repellent may be applied to the fiber substrate by a cleaning method, for example, applied to the fiber substrate in a washing application or a dry cleaning method, etc.

[0330] The fiber substrate to be treated may be cloth, which includes woven fabrics (woven cloth), knitted fabrics (knitted cloth) and non-woven fabrics, cloth in the form of clothing items and carpets, etc., but may also be fibers or yarns or intermediate fiber products (e.g., sliver or roving, etc.). The water repellent of the present disclosure is particularly effective in making fiber products (e.g., synthetic fibers) water repellent.

[0331] The fibers constituting the fibrous substrate may be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers or inorganic fibers. The fibers may be used alone or in combination of two or more kinds.

[0332] Examples of natural fibers are cellulose-based fibers such as cotton, linen, pulp, etc., chitin, chitosan, wool, and silk. Specific examples of wood pulp are mechanical pulps such as groundwood pulp (GP), pressure rise groundwood pulp (PGW), thermomechanical pulp (TMP), etc., chemical pulps such as softwood unbleached kraft pulp (HNKP; N wood), softwood bleached kraft pulp (NBKP; N wood, NB wood), hardwood unbleached kraft pulp (LUKP; L wood), hardwood bleached kraft pulp (LBKP, L wood), etc., wastepaper pulps such as deinking pulp (DIP), waste pulp (WP), and semi-chemical pulp (CP), etc.

[0333] Examples of synthetic fibers are polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, copolymerized polyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, nylon 46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, polyvinyl chloride. Examples of semi-synthetic fibers are acetate, triacetate. Examples of regenerated fibers are rayon, cupra, polynosic rayon, lyocell, tencel. Examples of inorganic fibers are glass fibers, carbon fibers.

[0334] Alternatively, the fibrous substrate may be leather. The production polymer may be applied to the leather from an aqueous solution or an aqueous emulsion at various stages of leather processing, for example, during the wet processing of the leather or during the finishing of the leather, in order to make the leather hydrophobic and oleophobic. Alternatively, the fibrous substrate may be paper. The production polymer may be applied to the pre-formed paper, or may be applied at various stages of papermaking, for example, during the drying period of the paper.

[0335] "Treatment" means applying a water repellent to a substrate by means such as dipping, spraying, coating, etc. By the treatment, the polymer which is the active ingredient of the water repellent penetrates into the inside of the substrate and / or adheres to the surface of the substrate. In other words, by the treatment, a substrate (for example, a textile product) to which the polymer in the water repellent of the present disclosure adheres is obtained. Such a substrate is a textile product having water repellency, that is, a water-repellent textile product.

[0336] [Pretreatment of Fiber Substrate] The fiber substrate may be pretreated before being treated with the water repellent of the present disclosure. By performing the pretreatment of the fiber substrate, excellent fastness can be imparted to the fiber substrate after being treated with the water repellent.

[0337] Examples of the pretreatment of the fiber substrate include cationization treatment by reaction with a reactive quaternary ammonium salt, anionic treatment such as sulfonation, carboxylation, phosphorylation, etc., acetylation treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, polymer coating treatment, etc. after the anionic treatment.

[0338] The method for pretreating the fiber substrate is not limited, but the fiber substrate can be pretreated by a conventionally known method. The pretreatment liquid can be dispersed and diluted in an organic solvent or water as necessary, and adhered to the surface of the fiber substrate by a known method such as dip coating, spray coating, foam coating, etc., and then dried. The pH and temperature of the pretreatment liquid etc. may be adjusted according to the required degree of treatment. As an example of the method for pretreating the fiber substrate, the method for pretreating the fiber substrate with a hydrocarbon-based water repellent will be described in detail.

[0339] The pretreatment method of the fiber substrate is to attach a monovalent group represented by -SO3M 1 (wherein M 1 represents a monovalent cation), a monovalent group represented by -COOM 2 (wherein M 2 represents a monovalent cation), and -O-P(O)(OX 1 )(OX 2 (wherein X 1 and X 2It may also include a step of imparting at least one functional group (hereinafter, may also be referred to as "specific functional group") selected from the group consisting of monovalent groups represented by (each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

[0340] M 1 Examples of M include H, K, Na, or an ammonium ion which may have a substituent. 2 Examples of X include H, K, Na, or an ammonium ion which may have a substituent. 1 or X 2 When 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.

[0341] The fiber containing the above specific functional group (hereinafter, may also be referred to as "functional group-containing fiber") can be prepared, for example, by the following method. (i) A compound having the above specific functional group is attached to the fiber material. Note that the attachment of the compound may be in a state where a part of the compound and a part of the fiber are chemically bonded within the range where a sufficient amount of the above specific functional group remains. (ii) A fiber in which the above specific functional group is directly introduced into the material constituting the fiber is prepared.

[0342] In the case of (i), for example, a functional group-containing fiber can be obtained by a functional group introduction step of treating the fiber material with a pretreatment liquid containing one or more compounds having the above specific functional group.

[0343] The material of the fiber material is not particularly limited, and examples include natural fibers such as cotton, hemp, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The form of the fiber material may be any form such as fiber (tow, sliver, etc.), yarn, knitted fabric (including cross-knitting), woven fabric (including cross-weaving), non-woven fabric, and paper.

[0344] In the present embodiment, from the viewpoint of improving the water repellency of the obtained fiber product, it is preferable to use a fiber material containing polyamide and polyester as raw materials. 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.

[0345] The above -SO3M 1 As the compound having, a phenolic polymer can be used. Such phenolic polymers include, for example, those containing at least one compound represented by the following general formula.

[0346]

Chemical formula

[0347]

Chemical formula

[0348] As the above M 3 , examples include H, K, Na, or an ammonium ion that may have a substituent.

[0349] As the above M 4 , examples include H, K, Na, or an ammonium ion that may have a substituent.

[0350] The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0351] The above -COOM 2Examples of the compound having [the relevant property] include polycarboxylic acid polymers.

[0352] As the polycarboxylic acid polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, etc. as monomers, or a commercially available one can be used.

[0353] Examples of the method for producing the polycarboxylic acid polymer include a method of adding a radical polymerization initiator to an aqueous solution of the above monomers and / or their salts and heating and reacting at 30 to 150 °C for 2 to 5 hours. At this time, alcohols such as methanol, ethanol, isopropyl alcohol, etc. or aqueous solvents such as acetone may be added to the aqueous solution of the above monomers and / or their salts. Examples of the radical polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, etc., redox polymerization initiators by combinations of persulfates and sodium bisulfite, etc., hydrogen peroxide, water-soluble azo polymerization initiators, etc. These radical polymerization initiators may be used alone or in combination of two or more. Further, during radical polymerization, a chain transfer agent (for example, octyl thioglycolate) may be added for the purpose of adjusting the degree of polymerization.

[0354] For radical polymerization, monomers copolymerizable with the above monomers can be used. Examples of the copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, vinyl acetate, etc., acrylamide, acrylates, methacrylates, etc. Acrylates and methacrylates preferably have a hydrocarbon group with 1 to 3 carbon atoms which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, propyl methacrylate, etc. These copolymerizable monomers may be used alone or in combination of two or more.

[0355] The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized by an alkali metal, an amine compound, or the like. Examples of the alkali metal include sodium, potassium, lithium, etc., and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, triethanolamine, etc.

[0356] From the viewpoint of obtaining a fiber product with good water repellency, the weight average molecular weight of the polycarboxylic acid polymer is preferably 1000 to 20000, more preferably 3000 to 15000.

[0357] As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (manufactured by Nihon Kayaku Co., Ltd., trade name) and "Cellopol PC-300" (manufactured by Sanyo Chemical Industries, Ltd., trade name) can be used.

[0358] The above -O-P(O)(OX 1 )(OX 2 ) Examples of the compound having are, for example, phosphate ester compounds represented by the following general formula.

Chemical formula

[0359] As the above phosphate ester compound, a phosphate monoester, diester, and triester in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and a mixture thereof can be used.

[0360] From the viewpoint of obtaining a fiber product with good water repellency, it is preferable to use lauryl phosphate ester and decyl phosphate ester.

[0361] As the phosphate ester compound, commercially available products such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name) can be used, for example.

[0362] The pretreatment liquid containing one or more kinds of the compounds having the specific functional group can be, for example, an aqueous solution of the above-described compounds. Further, the pretreatment liquid may contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0363] Examples of the method for treating the fiber material with the above pretreatment liquid include padding treatment, dipping treatment, spraying treatment, and coating treatment. As the padding treatment, for example, the method using a padding apparatus described on pages 396 to 397 of the Fiber Dyeing Processing Dictionary (1963, published by Nikkansen) or pages 256 to 260 of Color Dyeing Chemistry III (1975, published by Jitsugyo Shuppan Co., Ltd.) can be mentioned. As the coating treatment, for example, the method using a coating machine described on pages 473 to 477 of the General List of Dyeing Finishing Equipment (1981, published by Sen'i Sha) can be mentioned. As the dipping treatment, for example, the method using a batch dyeing machine described on pages 196 to 247 of the General List of Dyeing Finishing Equipment (1981, published by Sen'i Sha) can be mentioned, and a liquid flow dyeing machine, an air flow dyeing machine, a drum dyeing machine, a winch dyeing machine, a washer dyeing machine, a cheese dyeing machine, etc. can be used. As the spraying treatment, for example, an air spray that atomizes the treatment liquid with compressed air and sprays it, or a method using an air spray of a hydraulic atomization method can be mentioned. The treatment conditions such as the concentration of the treatment liquid at this time and the heat treatment after application can be appropriately adjusted in consideration of various conditions such as the purpose and performance. Further, when the pretreatment liquid contains water, it is preferable to dry it in order to remove the water after adhering it to the fiber material. The drying method is not particularly limited, and either a dry heat method or a wet heat method may be used. The drying temperature is also not particularly limited, but for example, it may be dried at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes after drying.

[0364] In the case where the fiber material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as dyeing. However, when performing reduction soaping, since the compound having the above specific functional group adsorbed during the process (for example, phenolic polymer compound, etc.) may fall off, it is preferably carried out after reduction soaping after dyeing.

[0365] The treatment temperature in the dipping treatment can be 60 to 130 °C. The treatment time can be 5 to 60 minutes.

[0366] In the functional group introduction step with the pretreatment liquid, it is preferable to carry out the treatment in such an amount that the adhesion amount of the compound having the above specific functional group becomes 1.0 to 7.0 parts by weight with respect to 100 parts by weight of the fiber material. Within this range, both durable water repellency and texture can be achieved at a high level.

[0367] The pretreatment liquid is preferably adjusted to a pH of 3 to 5. For pH adjustment, pH adjusters such as acetic acid and malic acid can be used.

[0368] In the pretreatment liquid, salts can also be used in combination in order to effectively adsorb the compound having the above specific functional group to the fiber material by the salting-out effect. Examples of salts that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0369] In the functional group introduction step with the pretreatment liquid, it is preferable to remove the compound having the above specific functional group that has been treated excessively. Examples of the removal method include the method by water washing. By performing sufficient removal, it is possible to suppress the inhibition of the expression of water repellency in the subsequent water repellent processing, and in addition, the texture of the obtained fiber product becomes good. Further, the obtained functional group-containing fiber is preferably dried sufficiently before contacting with the hydrocarbon-based water repellent.

[0370] (ii) Examples of the fiber in which the above specific functional group is directly introduced into the material constituting the fiber include cation-dyeable polyester (CD-PET).

[0371] From the viewpoint of obtaining a fiber product with good water repellency, the zeta potential of the surface of the functional group-containing fiber is preferably -100 to -0.1 mV, and more preferably -50 to -1 mV. The zeta potential of the fiber surface can be measured, for example, with a zeta potential and particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0372] As a method for treating the pulp base material, an internal addition treatment method in which a water repellent is added to the pulp before papermaking (for example, pulp slurry), or an external addition treatment method in which a water repellent is applied to the pulp after papermaking (for example, pulp product) can be used. Examples of the internal addition treatment method include mixing, dipping, etc., and may include a step of adding a water repellent to the pulp slurry and stirring and mixing. Examples of the external addition treatment method include spraying, coating, etc., and specifically include a pond type two-roll size press, a gate roll type, and a rod metering size press, etc. The treatment may be an external addition treatment or an internal addition treatment. For example, when the pulp base material is paper, it may be coated on the paper, or a solution may be adhered or sprayed on the paper, or it may be treated by mixing with the pulp slurry before papermaking.

[0373] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims.

Examples

[0374] Hereinafter, the examples of the present disclosure will be specifically described, but the examples do not limit the present disclosure.

[0375] <Test method> The test procedure is as follows.

[0376] 〔Water repellency〕 The water repellency of the test treatment cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). The water repellency was evaluated according to the criteria shown below. A higher score indicates better water repellency, and intermediate values (95, 85, 75, 65, 55) were assigned depending on the state. 100 No wetness or water droplet adhesion was observed on the surface. 90 The surface was not wet, but adhesion of small water droplets was observed. 80 Wetness was observed on small individual water droplets on the surface. 70 Half of the surface showed wetness, and a state where small individual wetness penetrated the cloth was observed. 50 Wetness was observed over the entire surface. 0 Wetness was observed on the entire surface and the back surface.

[0377] 〔Light oil repellency〕 An oil obtained by blending oleic acid / PEG at 1:9 was dropped onto the test treatment cloth, and the oil repellency performance was evaluated in the following 4 levels. Intermediate values (B+, B-, C+, C-) were assigned depending on the state. A: The liquid droplet is transparent (not wet) and round. B: The edge or bottom of the liquid droplet is slightly darkened and rounded. C: Some penetration of the liquid droplet into the fabric was observed. D: The liquid droplet has completely penetrated.

[0378] 〔Chalk mark resistance〕 Each test cloth was placed on a flat surface, and the surface of the test cloth was gently scratched with a fingernail. The scratch marks left by the fingernail like chalk were visually judged and evaluated. ◎○: The mark is hardly visible. ○: The mark is barely visible. 〇△: The mark is faintly visible. △: The mark is visible. △×: The mark is somewhat darkly visible.

[0379] Si-based monomer (A) Based on WO2020 / 142441, the Si-based monomer (A) shown below was obtained. TIFF0007712587000020.tif50101

[0380] Si-based monomer (B) Based on WO2020 / 142474, the Si-based monomer (B) shown below was obtained. TIFF0007712587000021.tif49104

[0381] Si-based monomer (C) [Preparation of Monomer] (Synthesis of Intermediate 1) A four-necked flask was equipped with a thermometer, a dropping funnel, and a nitrogen line, and the flask was immersed in an ice bath. Subsequently, 14.74 g of 1,1,1,3,3-pentamethyldisiloxane, 0.04 g of tris(pentafluorophenyl)borane, and 30 mL of toluene were added to the flask, and the solution was stirred. After purging the inside of the flask with a nitrogen atmosphere, 5.1 mL of (3-chloropropyl)diethoxy(methyl)silane and 10 mL of toluene were placed in the dropping funnel, and this solution was slowly added to the flask. After completion of the dropping, the ice bath was removed, and stirring was continued at room temperature for 6 hours. After confirming the Si-OEt conversion by 1H-NMR, neutral alumina was added to the flask and stirred for 30 minutes. The stirred alumina mixture was filtered through a 0.45 μm filter to obtain a solution. The solvent of the obtained solution was distilled off using a rotary evaporator to obtain a transparent liquid intermediate 1. Intermediate 1 was evaluated by 1H-NMR and GC. (Synthesis of Si-based Monomer (C)) A four-necked flask was equipped with a thermometer, a dropping funnel, and a nitrogen line, and the flask was immersed in an ice bath. Subsequently, 0.01 g of butylated hydroxytoluene, 0.36 g of potassium iodide, 0.98 g of sodium acrylate, 40 mL of dimethylformamide, and 5 g of intermediate 1 were added to the flask to obtain a mixture. After purging the inside of the flask with a nitrogen atmosphere, the flask was heated to 120 °C, and the mixture was stirred for 5 hours. Then, the flask was cooled to 50 °C, and the mixture was washed with water using a separatory funnel to obtain a yellow liquid. This was dried over sodium sulfate, and the obtained mixture was filtered to obtain Si-based monomer (C) as a transparent liquid. Si-based monomer (C) was evaluated by 1H-NMR and GC. TIFF0007712587000022.tif80167

[0382] [Preparation of Raw Materials] [Manufacturing Example of Silicone Polymer-Containing Aqueous Dispersion] Manufacturing Example 1 In a 500 ml plastic container, 15 g of a water-soluble glycol-based solvent as an organic solvent, 100 g of pure water as a liquid medium, 100 g of Si-based monomer (A), 4 g of sorbitan fatty acid ester, 4 g of a cationic emulsifier, and 3 g of polyoxyethylene alkyl ether as surfactants were charged, heated to 80°C, stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed with ultrasonic waves for 15 minutes. Next, this mixture was transferred to a 500 ml four-neck separable flask, purged with nitrogen, and 0.1 g of lauryl mercaptan was charged as a chain transfer agent. Further, 0.3 g of an azo group-containing water-soluble initiator was added as a polymerization initiator, the temperature was raised to 60°C, and the reaction was carried out for 4 hours to obtain an aqueous dispersion of a silicone polymer (water-repellent resin). This dispersion was further diluted with pure water to prepare an aqueous dispersion containing 30% non-volatile content of a silicone polymer (specifically, an aqueous dispersion containing a silicone polymer, a surfactant, and a liquid medium).

[0383] Manufacturing Example 2 In a 500 ml plastic container, 15 g of a water-soluble glycol-based solvent as an organic solvent, 100 g of pure water as a liquid medium, 75 g of Si-based monomer (A), 25 g of stearyl acrylate as a long-chain aliphatic hydrocarbon group-containing (meth)acrylate, 4 g of sorbitan fatty acid ester, 4 g of a cationic emulsifier, and 3 g of polyoxyethylene alkyl ether as surfactants were charged, heated to 80°C, stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed with ultrasonic waves for 15 minutes. Next, this mixture was transferred to a 500-ml four-neck separable flask. After purging with nitrogen, 0.1 g of lauryl mercaptan was charged as a chain transfer agent. Further, 0.3 g of an azo group-containing water-soluble initiator was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 4 hours to obtain an aqueous dispersion of a silicone-acrylic polymer (water-repellent resin). This dispersion was further diluted with pure water to prepare an aqueous dispersion containing 30% by solid content of the silicone-acrylic polymer (specifically, an aqueous dispersion containing a silicone-acrylic polymer, a surfactant, and a liquid medium).

[0384] Production Examples 3, 4, 9 to 11 According to Table 1, an aqueous dispersion containing a silicone-acrylic polymer, a surfactant, and a liquid medium was prepared in the same manner as in Production Example 1, except that the formulation was changed.

[0385] Production Example 5 Into a 500-ml plastic container, 15 g of a water-soluble glycol-based solvent as an organic solvent, 100 g of pure water as a liquid medium, 30 g of an Si-based monomer (A), 56 g of stearyl acrylate as a (meth)acrylate containing a long-chain aliphatic hydrocarbon group, 4 g of sorbitan fatty acid ester, 4 g of a cationic emulsifier, and 3 g of a polyoxyethylene alkyl ether were charged as a surfactant. The mixture was heated to 80°C, stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed with ultrasonic waves for 15 minutes. Next, this mixture was transferred to a 500-ml autoclave. After purging with nitrogen, 0.1 g of lauryl mercaptan and 14 g of vinyl chloride were charged as a chain transfer agent. Further, 0.3 g of an azo group-containing water-soluble initiator was added as a polymerization initiator, and the temperature was raised to 60°C and reacted for 4 hours to obtain an aqueous dispersion of a silicone-acrylic polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion having a non-volatile concentration of 30%.

[0386] Production Examples 6 to 8 According to Table 1, an aqueous dispersion containing a silicone-acrylic polymer, a surfactant, and a liquid medium was prepared in the same manner as in Production Example 5, except that the formulation was changed.

[0387] Comparative Production Examples 1 to 3 A comparative aqueous dispersion was prepared in the same manner as in Production Example 1, except that the formulation was changed according to Table 1.

[0388] [Table 1] The numbers in the table are the charged amounts (g)

[0389] Example 1 An aqueous dispersion with a non-volatile content concentration of 30% prepared in Production Example 1 was diluted with tap water to prepare a treatment liquid with a non-volatile content concentration of 1.5%. A polyester cloth, a nylon cloth, and a polyester / spandex cloth were immersed in this treatment liquid and then wrung out with a mangle. This treated cloth was passed through a pin tenter at 170°C for 1 minute for drying and curing. The test cloth thus treated was evaluated for the water repellency, light oil repellency, and chalk mark properties described above. The evaluation results are shown in Table 2.

[0390] Examples 2 to 11 A treatment liquid with a non-volatile content concentration of 1.5% was prepared in the same manner as in Example 1, except that the formulation was changed according to Table 2. Using this treatment liquid, the cloth was treated in the same manner as in Example 1, and the water repellency, light oil repellency, and chalk mark properties were evaluated. The results are shown in Table 2.

[0391] Comparative Examples 1 to 3 A treatment liquid with a non-volatile content concentration of 1.5% was prepared in the same manner as in Example 1, except that the formulation was changed according to Table 2. Using this treatment liquid, the cloth was treated in the same manner as in Example 1, and the water repellency, light oil repellency, and chalk mark properties were evaluated. The results are shown in Table 2.

[0392] [Table 2]

Industrial Applicability

[0393] The polymers of the present disclosure can be used to impart good anti-chalking properties, water repellency, and oil repellency to various products (e.g., paper, textile products, etc.).

Claims

1. The following formula (1-1) or formula (1-2): CR ａ R ｂ =C(−R ｃ )−X−CY ３－ｎ Z ｎ (1−1) CR ａ R ｂ =C(−R ｃ )−X−NY ２－ｎ Z ｎ (1−2) [In each formula: R ａ , R ｂ , and R ｃ are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, X is a single bond or a divalent group, Y is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 or 2, Z is, independently of each other, -Z １ -SiZ ２ ３ and Z １ is a single bond or a divalent group, Z ２ are each independently -(O-Si(-OSiZ ２１ ３ ) ２ ) ｐ -O-SiZ ２２ ３ wherein Z ２１ is, independently of one another, a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ ２１１ ３ wherein Z ２１１ is, independently of one another, a hydrocarbon group having 1 to 10 carbon atoms, Z ２２ is, independently of each other, a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ ２２１ ３ wherein Z ２２１ is, independently of one another, a hydrocarbon group having 1 to 10 carbon atoms, p is an integer of 0 to 196, In the formula (1-1), at least one of X and Z1 has a hydrocarbon group having 3 or more carbon atoms.] A water-repellent agent for fibers containing a polymer containing a repeating unit derived from a monomer (1) represented by the formula.

2. X is a divalent group composed of one or more selected from the group consisting of X １ and X ２ and is composed of one or more selected from the group consisting of X １ is a group composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ -, -NR'-, and -C(OR')R'- (wherein R' is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). X ２ The water-repellent agent for fibers according to claim 1, wherein X is a hydrocarbon group having 1 to 22 carbon atoms which may be directly bonded or may have a substituent.

3. X is -X １ -X ２ The water-repellent agent for fibers according to claim 2, which is -.

4. Z １ is a divalent group composed of one or more selected from the group consisting of Z １１ and Z １２ and is composed of one or more selected from the group consisting of Z １１ is a group composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ -, -NR'-, and -C(OR')R'- (wherein R' is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). Z １２ The water repellent for fibers according to claim 1, wherein Z is a hydrocarbon group having 1 to 22 carbon atoms which may have a direct bond or a substituent.

5. Z １ The water-repellent agent for fibers according to claim 4, wherein Z is a hydrocarbon group having 1 to 22 carbon atoms which may be directly bonded or may have a substituent.

6. The water-repellent agent for fibers according to Claim 1, wherein n is 1.

7. The OSiZ ２１ ３ Among the three Zs ２１ At least two of the Zs ２１ Are -OSiZ ２１１ The water repellent for fibers according to claim 1, wherein said at least two of the Zs are -OSiZ.

8. said SiZ ２２ ３ Among the three Zs in ２２ at least two Zs of ２２ are -OSiZ ２２１ The water repellent for fibers according to claim 1, wherein.

9. The water-repellent agent for fibers according to Claim 1, further containing a repeating unit derived from a hydrophobic monomer (2) having a hydrocarbon group having 6 to 40 carbon atoms.

10. The water-repellent agent for fibers according to Claim 9, wherein the hydrocarbon group in the hydrophobic monomer (2) is a linear alkyl group having 10 or more carbon atoms.

11. The hydrophobic monomer (2) has the following formula: CH ２ =C(-R ｂ )-C(=O)-R ｃ -(R ｄ ) ｋ (2) [In the formula, R ｂ is a hydrogen atom, a monovalent organic group or a halogen atom, R ｃ is a divalent to tetravalent group having 1 carbon atom and being directly bonded, -C ６ H ４ -, -O-, -S-, -C(=O)-, -S(=O) ２ -, and -NR Ｃ１ -(R Ｃ１ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), and is a divalent to tetravalent group composed of at least one selected therefrom, k is 1 to 3, R ｄ is a hydrocarbon group having 6 to 40 carbon atoms. The water-repellent agent for fibers according to Claim 9, which is a monomer represented by the formula.

12. The water-repellent agent for fibers according to Claim 9, wherein the content of the hydrophobic monomer (2) is 20% by weight or more based on the polymer.

13. The water-repellent agent for fibers according to Claim 12, wherein the content of the monomer unit (1) is 0.5% by weight or more based on the polymer.

14. The water-repellent agent for fibers according to Claim 13, wherein the weight ratio of the monomer unit (1) represented by the monomer unit (1) / the monomer unit (2) in the polymer is 0.005 to 0.

40.

15. The water-repellent agent for fibers according to Claim 1, which is non-fluorine-based.

16. The monomer (1) has the formula: CR ａ R ｂ =C(−R ｃ )−X−NY ２－ｎ Z ｎ (1−2) wherein, R ａ and R ｂ are each independently a hydrogen atom, R ｃ is each independently an alkyl group having 1 to 3 carbon atoms, X is -C(=O)-O-(CH ２ ), ｒ - or -C(=O)-NR'-(CH ２ ), ｒ - (wherein each R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). r is independently an integer of 1 to 22, The water-repellent agent for fibers according to Claim 1.

17. Y is independently an alkyl group having 1 to 3 carbon atoms, n is 1, Z １ is -(CH ２ ) ｑ - and q is an integer of 1 to 22, p is 0, Z ２２ is, independently of each other, an alkyl group having 1 to 3 carbon atoms or -OSiZ ２２１ ３ wherein Z ２２１ The water-repellent agent for fibers according to claim 1, wherein Z is independently an alkyl group having 1 to 3 carbon atoms.

18. The monomer (1) has the formula: CR ａ R ｂ =C(−R ｃ )−X−NY ２－ｎ Z ｎ (1 - 2) wherein, R ａ and R ｂ are each independently a hydrogen atom, R ｃ is each independently an alkyl group having 1 to 3 carbon atoms, X is -C(=O)-O-(CH ２ ), ｒ - or -C(=O)-NR'-(CH ２ ), ｒ - (wherein each R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). r is independently an integer of 1 to 22, Y is independently an alkyl group having 1 to 3 carbon atoms, n is 1, Z １ is -(CH ２ ) ｑ -, and q is an integer of 1 to 22, p is 0, Z ２２ is, independently of one another, an alkyl group having 1 to 3 carbon atoms or -OSiZ ２２１ ３ and Z ２２１ The water repellent for fibers according to claim 1, wherein each of them is independently an alkyl group having 1 to 3 carbon atoms.

19. The method for producing a water-repellent agent for fibers according to claim 1, comprising a step of reacting a monomer (1) in a medium containing at least one selected from the group consisting of a urethane, paraffin wax, silica, and silicone to obtain a polymer.

20. A water-repellent fiber product in which the polymer according to any one of claims 1 to 18 is adhered to a fiber substrate.

21. On the fiber substrate -SO ３ M １ (In the formula, 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), and the water-repellent fiber product according to claim 20, to which one or more functional groups selected from the group consisting of monovalent groups represented by are attached.

22. A method for producing a water-repellent fiber product, comprising applying the water-repellent agent for fibers according to any one of claims 1 to 18 to a fiber substrate.

23. Before applying the water-repellent agent to the fiber substrate, on the fiber substrate -SO ３ M １ (wherein M １ represents a monovalent cation) a monovalent group represented by -COOM ２ (wherein M ２ represents a monovalent cation) and 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), and the method for producing a water-repellent fiber product according to claim 22, comprising a step of imparting one or more functional groups selected from the group consisting of monovalent groups represented by

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