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

Abstract

To provide a polymer which can impart superior water repellency and oil repellency to a substrate.SOLUTION: Disclosed is a polymer for use in a water repellent, which includes a repeating unit that is derived from a monomer (1) represented by the following formula: CRaRb=C(-Rc)-X-SiY3-nZn. [In the formula: Ra, Rb, and Rc each represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, X represents a single bond or a divalent group, Y represents a hydrocarbon group having 1 to 10 carbon atoms, n represents an integer of 1 or 2, and Z represents -(O-SiZ12)p-(CH2)q-Z2-Si(-OSiZ33)2Z4, Z1 represents a hydrocarbon group having 1 to 10 carbon atoms or the like, Z2 represents O or CH2, Z3 represents a hydrocarbon group having 1 to 10 carbon atoms or the like, Z4 represents a hydrocarbon group having 1 to 10 carbon atoms or the like, p represents an integer of 0 to 196, and q represents an integer of 0 to 10].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to polymers, water repellents, textiles, and methods for making textiles. [Background technology]

[0002] Non-fluorine-based water repellents have been developed to impart water repellency to substrates (especially textile products). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2023 / 033719 Summary of the Invention [Problem to be solved by the invention]

[0004] In Patent Document 1, chalk mark resistance is improved by treating an object to be treated, such as a textile product, with a composition prepared by dissolving in a solvent a silicone-containing copolymer that includes structural units derived from a (meth)acrylic acid alkyl ester monomer; however, the water repellency and oil repellency are insufficient.

[0005] An object of the present disclosure is to provide a polymer that can impart excellent water and oil repellency to a substrate. [Means for solving the problem]

[0006] The present disclosure includes the following aspects: [Item 1] A polymer for a water repellent agent, the polymer having the following formula: CR a R b =C(-R c )-X-SiY 3-n Z n [In formula: R a , R b , and R ceach independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, X is a single bond or a divalent group; Each Y is independently a hydrocarbon group having 1 to 10 carbon atoms; n is an integer of 1 or 2, Each Z is independently -(O-SiZ 1 2) p -(CH2) q -Z 2 -Si(-OSiZ 3 3) 2Z 4 and Z 1 each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 11 3, Z 11 each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 111 3, Z 111 are each independently a hydrocarbon group having 1 to 10 carbon atoms, Z 2 is O or CH2, Z 3 each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 31 3, Z 31 are each independently a hydrocarbon group having 1 to 10 carbon atoms, Z 4 each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 41 3, Z 41 are each independently a hydrocarbon group having 1 to 10 carbon atoms, p is an integer from 0 to 196; and q is an integer from 0 to 10. A polymer comprising a repeating unit derived from a monomer (1) represented by the formula: [Term 2] X is X 1 and X 2 is a divalent group consisting of one or more members selected from the group consisting of X1 is a group consisting 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 independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms); X 2 Item 2. The polymer according to item 1, wherein is a direct bond or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent. [Term 3] X is -X 1 -X 2 Item 3. The polymer according to item 1 or 2, wherein [Item 4] The polymer according to any one of Items 1 to 3, wherein n is 1. [Section 5] Z 1 each independently represents a hydrocarbon group having 1 to 10 carbon atoms. [Item 6] The polymer according to any one of Items 1 to 5, wherein n is 2. [Item 7] The polymer according to item 6, wherein p is 0. [Item 8] The polymer according to any one of Items 1 to 7, further comprising a repeating unit derived from a hydrophobic monomer (2) having a hydrocarbon group having 2 to 40 carbon atoms. [Item 9] The polymer according to Item 8, wherein the hydrocarbon group in the hydrophobic monomer (2) is a linear alkyl group having 10 or more carbon atoms. [Item 10] 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 represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2-, or -NR C1 -(R C1 is a divalent to tetravalent group consisting of at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms, k is 1 to 3; R d is a hydrocarbon group having 2 to 40 carbon atoms. Item 10. The polymer according to item 8 or 9, wherein the monomer is represented by the formula: [Item 11] The polymer according to any one of Items 8 to 10, wherein the content of the hydrophobic monomer (2) is 20% by weight or more based on the polymer. [Item 12] The polymer according to item 11, wherein the content of the monomer unit (1) is 0.5% by weight or more based on the polymer. [Item 13] The polymer according to item 11, wherein a 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 14] The polymer according to item 13, wherein the content of the monomer unit (1) is 5% by weight or more based on the polymer. [Item 15] The polymer according to any one of Items 1 to 14, which is a non-fluorinated polymer. [Section 16] 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, each R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), Item 2. The polymer according to item 1, wherein each r is independently an integer of 1 to 22. [Section 17] Each Y is independently an alkyl group having 1 to 3 carbon atoms; n is 2, p is 0, q is 0, Z 2 is -O-, Z 3 each independently represents an alkyl group having 1 to 3 carbon atoms or -OSiZ 31 3, Z 31are each independently an alkyl group having 1 to 3 carbon atoms, Z 4 each independently represents an alkyl group having 1 to 3 carbon atoms or -OSiZ 41 3, Z 41 and each independently represent an alkyl group having 1 to 3 carbon atoms. [Section 18] 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, each R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), Each r is independently an integer from 1 to 22; Each Y is independently an alkyl group having 1 to 3 carbon atoms; n is 2, p is 0, q is 0, Z 2 is -O-, Z 3 each independently represents an alkyl group having 1 to 3 carbon atoms or -OSiZ 31 3, Z 31 are each independently an alkyl group having 1 to 3 carbon atoms, Z 4 each independently represents an alkyl group having 1 to 3 carbon atoms or -OSiZ 41 3, Z 41 and each independently represent an alkyl group having 1 to 3 carbon atoms. [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 comprising the polymer according to any one of items 1 to 18, or the composition according to item 19 or 20. [Item 22] A method for producing the water repellent according to Item 21, comprising a step of reacting the monomer (1) in a medium containing the monomer (1) and at least one selected from the group consisting of urethane, paraffin wax, silica, and silicone to obtain a polymer. [Item 23] A water-repellent textile product comprising a textile substrate to which the polymer according to any one of items 1 to 18 is adhered. [Item 24] The fiber base material is -SO3M 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms), [Item 25] A method for producing a water-repellent textile product, comprising applying the water repellent according to item 21 to a textile substrate. [Item 26] Before applying the water repellent to the fiber substrate, -SO3M 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. Effect of the Invention

[0007] The polymers in the present disclosure can impart excellent water and oil repellency to a substrate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] <Terminology> As used herein, the term "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. The term "n-valent organic group" refers to a group having n valences containing carbon, and the term "organic group" refers to a group containing carbon. Such organic groups are not particularly limited, and may be hydrocarbon groups or derivatives thereof. The term "hydrocarbon group derivatives" refers to groups having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the end or molecular chain of the hydrocarbon group.

[0009] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but may be a C1-20 hydrocarbon group, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, etc. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. In addition, the hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents.

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

[0011] It should be understood that the chemical structures illustrated herein do not encompass chemical structures that would be recognized by those of ordinary skill in the art as being chemically impossible or extremely unstable.

[0012] <Polymer> The polymer of the present disclosure is a polymer for a water repellent agent, and has the following formula: CR a R b =C(-R c )-C(=O)-O-(CH2) α -SiY 3-n Z n [In formula: R a , R b , and R c each independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, X is a single bond or a divalent group; Each Y is independently a hydrocarbon group having 1 to 10 carbon atoms; n is an integer of 1 or 2, Each Z is independently -(O-SiZ 1 2) p -(CH2) q -Z 2 -Si(-OSiZ 3 3) 2Z 4 and Z 1 each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 11 3, Z 11 each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 111 3, Z 111 are each independently a hydrocarbon group having 1 to 10 carbon atoms, Z 2 is O or CH2, Z 3 each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 31 3, Z 31are each independently a hydrocarbon group having 1 to 10 carbon atoms, Z 4 each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 41 3, Z 41 are each independently a hydrocarbon group having 1 to 10 carbon atoms, p is an integer from 0 to 196; and q is an integer from 0 to 10. The monomer (1) contains a repeating unit derived from the monomer (1).

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

[0014] By virtue of having the above characteristics, the polymer of the present disclosure can impart excellent water repellency and oil repellency to a substrate (for example, a fiber substrate or a paper substrate).

[0015] The polymer of the present disclosure may be a non-fluorine-based polymer. 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 repeat unit derived from monomer (1). Monomer (1) is represented by the following formula: CR a R b =C(-R c )-X-SiY 3-n Z n

[0017] [R a ] R a R is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. The hydrocarbon group having 1 to 5 carbon atoms may be a hydrocarbon group having 1 to 3 carbon atoms or may be a methyl group. a may be a hydrogen atom.

[0018] [R b ] R b R is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. The hydrocarbon group having 1 to 5 carbon atoms may be a hydrocarbon group having 1 to 3 carbon atoms or may be a methyl group. b may be a hydrogen atom.

[0019] [R c ] R c R 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, and more preferably a methyl group. 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 consisting of one or more members selected from the group consisting of X 1 is a group consisting of one or more selected from the group consisting of 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 (e.g., 1 to 5, 1 to 3, or 1 carbon atom)); X 2 may be a direct bond or an optionally substituted divalent hydrocarbon group having 1 to 22 carbon atoms.

[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. 1 is preferably not only a direct bond.

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

[0026] X 1 X is -O-, -C(=O)-, -S(=O)2-, -NR'-, and -C(OR')R'- (wherein R' is independently at each occurrence one or more selected from the group consisting of a hydrogen atom or a group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). 1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples include:

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

[0028] X 2 The number of carbon atoms in 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. 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.

[0029] The divalent hydrocarbon group may be a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon 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 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 2The hydrocarbon group in may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (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 the 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 A specific example of the formula is -(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 divalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon aromatic ring such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 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 halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the 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 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0034] [Example of X] An example of X is -X 1 -, -X 1 -X 2 -, -X 1 -X 2 -X 1 -, -X 1 -X 2 -X 1 -X 2 -, -X 2 -, -X 2 -X 1 -, -X 2 -X 1 -X 2 -, -X 2 -X 1 -X 2 -X 1 -, etc. Preferred examples of X include -X 1 -X 2 -, -X 2 -- are some examples.

[0035] Examples of X are: -O-(CH2) r -, -OC(=O)-(CH2) r -, -OC(=O)-O-(CH2) r -, -OC(=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 -)2nd class (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples 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] An example of X is -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), Each r is independently an integer of 1 to 22, 1 to 10, or 1 to 4.

[0037] X may be a direct bond or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent. Preferably, X may be a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent. The number of carbon atoms in 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 in 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 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 exhibit liquid repellency. For this reason, a structure with many branches and many -CH3 groups is preferable. On the other hand, a long-chain alkyl group of a certain length exhibits high liquid repellency due to its crystallinity. Therefore, it may be a branched hydrocarbon group (for example, a branched alkyl group), particularly a t-butyl group or an isopropyl group, a group with a multi-branched structure, or a long-chain hydrocarbon group (or a long-chain linear hydrocarbon group), for example, an alkyl group.

[0040] The carbon number of the hydrocarbon of 1 to 10 carbon atoms represented by Y may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. The carbon number of the hydrocarbon of 1 to 10 carbon atoms represented by 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 n may be 0 to 9, and 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, and is preferably a methyl group.

[0043] [n] n means the number of Z groups. n is an integer of 1 or 2.

[0044] [Z] Each Z is independently -(O-SiZ 1 2) p -(CH2) q -Z 2 -Si(-OSiZ 3 3) 2Z 4 Z is a group having a siloxane bond.

[0045] [Z 1 〕 Z 1 each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 11 The answer is 3.

[0046] Z 1 The carbon number of the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. 1 The carbon number 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. 1 may be a methyl group.

[0047] The above OSiZ 1 Two Zs in 2 1 At least one Z 1 -OSiZ 11 3. 1 Two Zs in 2 1 -OSiZ 11Or it may be a hydrocarbon group having 1 to 10 carbon atoms.

[0048] (Z 11 ) Z 11 each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 111 The answer is 3.

[0049] Z 11 The carbon number of the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. 11 The carbon number 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. 11 may be a methyl group.

[0050] The above OSiZ 11 The three Zs in 3 11 At least two of the Z 11 -OSiZ 111 The above-mentioned OSiZ 11 The three Zs in 3 11 All Z 11 -OSiZ 111 or a hydrocarbon group having 1 to 10 carbon atoms, 11 -OSiZ 111 It may be.

[0051] (Z 111 ) Z 111 are each independently a hydrocarbon group having 1 to 10 carbon atoms. 111 The carbon number of the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. 111 The carbon number 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. 111 may be a methyl group.

[0052] [Z 2 〕 Z 2 is -O- or -CH2-.

[0053] [Z 3 〕 Z 3 each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 31 The answer is 3.

[0054] Z 3 The carbon number of the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. 3 The carbon number 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. 3 may be an alkyl group having 1 to 3 carbon atoms. 3 may be a methyl group.

[0055] Above - OSiZ 3 The three Zs in 3 3 At least two of the Z 3 -OSiZ 31 The above-mentioned OSiZ 3 The three Zs in 3 3 All Z 3 -OSiZ 31 or a hydrocarbon group having 1 to 10 carbon atoms, 3 -OSiZ 31 It may be.

[0056] (Z 31 ) Z 31 are each independently a hydrocarbon group having 1 to 10 carbon atoms. 31 The carbon number of the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. 31 The carbon number 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. 31 may be an alkyl group having 1 to 3 carbon atoms. 31 may be a methyl group.

[0057] [Z 4 〕 Z 4 each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ 41 The answer is 3.

[0058] Z 4 The carbon number of the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. 4 The carbon number 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. 4 may be an alkyl group having 1 to 3 carbon atoms. 4 may be a methyl group.

[0059] (Z 41 ) Z 41 are each independently a hydrocarbon group having 1 to 10 carbon atoms. 41 The carbon number of the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. 41 The carbon number 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. 41 may be an alkyl group having 1 to 3 carbon atoms. 41 may be a methyl group.

[0060] [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.

[0061] The total value of p in the formula may not exceed 196.

[0062] In one embodiment, p is 0.

[0063] 〔q〕 q is an integer from 0 to 10. q may be 0 or more, 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and may be 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, or 5 or less.

[0064] In one embodiment, q is 0.

[0065] In one embodiment, q is 0.

[0066] The terminal portion of the monomer (1) of the present disclosure has a trialkylsiloxy group (—OSiR Si 3) may contain a trialkylsiloxy group-containing structure bonded thereto (R Si is a hydrocarbon group having 1 to 10 carbon atoms, which will be described in detail below.

[0067] The above-mentioned terminal Si atom refers to a trialkylsiloxy group (-OSiR Si 3) is composed of a trialkylsiloxy group (-OSiR Si 3) adjacent to and bonded to the Si atom. Note that the Si atom is not bound to an alkyl group (R Si ) may be bonded.

[0068] The trialkylsiloxy group (—OSiR Si 3) is an integer from 1 to 3. The terminal site of the monomer (1) of the present disclosure means the terminal site on the Z side in the above formula, and is the site located within Z.

[0069] Specifically, the terminal portion of the monomer (1) of the present disclosure is represented by the following formula: -Si(-OSiR Si 3) X R Si 3-X [In formula: R Si are each independently a hydrocarbon group having 1 to 10 carbon atoms, and x is an integer from 1 to 3. The compound may include a structure represented by the following formula:

[0070] R Si R is a hydrocarbon group having 1 to 10 carbon atoms. Si The number of carbon atoms in the hydrocarbon having 1 to 10 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, or 6 or more. Si The number of carbon atoms in 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. Si R may be an alkyl group having 1 to 3 carbon atoms. Si may be a methyl group.

[0071] x is an integer of 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.

[0072] The trialkylsiloxy group (-OSiR) bonded to the Si atom at the terminal of monomer (1) Si 3) As for -OSiZ, which was explained above 31 3 and -OSiZ 41 3 is an example.

[0073] [(1) Examples of monomers] The monomer (1) has the following formula: CH2=CCH3-C(=O)-R a6 -XZ [In formula: R a6 is -O- or -NH-, X is -(CH2) q - and q is an integer from 1 to 10, Z is for SiZ 2 3-m Z 3 m and Z 2 are each independently an alkyl group having 1 to 10 carbon atoms, m is an integer of 1 or 2, Z 3 are each independently -O-SiZ 33 3, Z 33each independently represents an alkyl group having 1 to 10 carbon atoms or -OSiZ 331 3, Z 331 are each independently an alkyl group having 1 to 10 carbon atoms.] The monomer may be represented by the formula:

[0074] R a6 is -O- or -NH-, preferably -O-.

[0075] X is -(CH2) q -It is. 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 be 10 or less, 9 or less, 8 or less, 6 or less, or 5 or less.

[0076] Z is for SiZ 2 3-m Z 3 m It is. m is an integer of 1 or 2.

[0077] Z 2 are each independently an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0078] Z 3 are each independently -O-SiZ 33 The answer is 3.

[0079] Z 33 each independently represents an alkyl group having 1 to 10 carbon atoms or -OSiZ 331 It is 3. Z 33 The hydrocarbon having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.

[0080] Z 331 are each independently an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0081] [(1) Examples of monomers] 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. TIFF2025076414000001.tif3467

[0082] TIFF2025076414000002.tif1562

[0083] The monomer (1) of the present disclosure can be produced in accordance with, for example, the contents described in JP 2019-89715 A. The monomer (1) of the present disclosure may be a commercially available product.

[0084] (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 having 2 to 40 carbon atoms.

[0085] 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, and more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, and preferably 10 or more, 12 or more, 14 or more, or 16 or more. The number of carbon atoms in the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and preferably 30 or less, 25 or less, or 20 or less.

[0086] 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 not having an amide group, a urea group, or a urethane group. When the monomer (2) contains such a group, the effects of the present disclosure can be exhibited well.

[0087] 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 represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2-, or -NR C1 -(R C1 is a divalent to tetravalent group consisting of at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms, k is 1 to 3; R d is a hydrocarbon group having 2 to 40 carbon atoms. It is a monomer represented by the formula:

[0088] [R b ] R b is a hydrogen atom, a monovalent organic group, or a halogen atom.

[0089] R b R may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. b Examples of R are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. b is preferably a hydrogen atom, a methyl group, or a chlorine atom. b More preferably, R is a methyl group. b By using a methyl group, higher liquid repellency can be obtained.b may be a hydrogen atom, particularly from the standpoint of reactivity.

[0090] [R c ] R c represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C6H4-, -O-, -S-, -C(=O)-, -S(=O)2-, or -NR C1 -(R C1 is a divalent to tetravalent group consisting of at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms, k is 1 to 3.

[0091] R c is preferably a divalent group. Examples of the divalent to tetravalent hydrocarbon group having 1 carbon atom include -CH2-, -CH= having a branched structure, and -C≡ having a branched structure.

[0092] R c -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, R Y each independently represents a direct bond, -O-, or -NR C11 -(R C11is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms) or -S(=O)2-, R X Ha-(CH2) m -(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l - (each 1 is independently an integer of 0 to 5, and -C6H4- is a phenylene group). R c It is preferred that is not exclusively a divalent hydrocarbon group.

[0093] R c Specific examples are -O-, -NH-, -OC(=O)-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -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 -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4- or -NH-(CH2) m -NH-C6H4-, wherein m is an integer of 1 to 5, particularly 2 or 4.

[0094] R c -O-, -NH-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -NH-C(=O)-NH- [In the formula, m is an integer of 1 to 5, particularly 2 or 4.] It is preferable that R c is -O-, -O-(CH2) m -OC(=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 It is more preferably -NH-C(=O)-.

[0095] [R d ] R d is a hydrocarbon group having 2 to 40 carbon atoms.

[0096] 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 -CH2- and is more likely to exhibit liquid repellency. For this reason, a structure with many branches and many -CH3 groups is preferred. On the other hand, long-chain alkyl groups of a certain length exhibit high liquid repellency due to their crystallinity. Therefore, it may be a branched hydrocarbon group (for example, a branched alkyl group), particularly a t-butyl group or an isopropyl group, a group with a multi-branched structure, or a long-chain hydrocarbon group (or a long-chain linear hydrocarbon group), for example, an alkyl group. R d The number of carbon atoms in R 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, and is preferably 10 or more. d may have 40 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 12 or less carbon atoms.

[0097] [k] k is 1, 2 or 3. c In the case where R has a tetravalent hydrocarbon group having one carbon atom, k=3. c In the case where R has a trivalent hydrocarbon group having one carbon atom, k=2. c does not have a trivalent or tetravalent hydrocarbon group having one carbon atom (for example, R c has (for example, 1 to 6) divalent hydrocarbon groups (-CH2-) having 1 carbon atom, then k=1.

[0098] Examples of monomer (2) are: Formula (a1): CH2=C(-Xa1 )-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-.] A monomer represented by the formula: Formula (a2): 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 each independently represents a direct bond or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -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 the formula:

[0099] (a1) Monomer The 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 the formula:

[0100] The monomer (a1) is Y a1 a long chain acrylate ester monomer in which Y is -O-; a1 is a long chain acrylamide monomer in which is -NH-. R a1 R is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. a1 In the above formula, the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 carbon atoms, and particularly preferably 18 to 22 carbon atoms. X a1 may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0101] Preferred specific examples of long chain acrylate ester monomers are lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha chloroacrylate, icosyl alpha chloroacrylate, and behenyl alpha chloroacrylate. Specific preferred examples of the long-chain acrylamide monomer are stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0102] (a2) Monomer The monomer (a2) is a monomer different from the monomer (a1). The monomer (a2) is a (meth)acrylate or (meth)acrylamide having at least one group 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 [In the formula, R a2are 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 each independently represents a direct bond or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-; Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2. The compound may be represented by the formula: Y a22 And / or Z may not be a direct bond. a22 and Z may not simultaneously be a direct bond.

[0103] R a2 R is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. a2 In the above formula, the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22 carbon atoms.

[0104] X a2 may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0105] Y a22 -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, each Y' is independently a direct bond, -O-, -NH-, or -S(=O)2-, R' is -(CH2) m-(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l - (each 1 is independently an integer of 0 to 5, and -C6H4- is a phenylene group). It may be.

[0106] Y a22 Specific examples include direct bond, -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S (=O)2-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m-O-C6H4-, -NH-(CH2) m -NH-C6H4- [In the formula, m is an integer of 1 to 5.] It is.

[0107] Y a22 is preferably -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-. Y a22 More preferably, Y is -NH-C(=O)-, -C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O- or -NH-C(=O)-NH-. a22 does not have to be a direct bond.

[0108] Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a straight-chain structure or a branched structure. The carbon number 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, and -CH2CH2CH2CH= having a branched structure. Z does not have to be a direct bond.

[0109] 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 -OC(=O)-NH-R a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m-NH-C(=O)-OR a2 , CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R a2 [wherein R 3 and X a2 has the same meaning as above.] Monomer (a2) is CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 It is particularly preferred that:

[0110] Monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or a hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate, such as lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, or behenyl isocyanate. Alternatively, the monomer (a2) can be produced by reacting a (meth)acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0111] Preferred examples of the monomer (2) are as follows: Stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha chloroacrylate, behenyl alpha 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 alpha chloroacrylate, stearamidoethyl (meth)acrylate, 2-stearamidoethyl acrylate, CH2=CHC(=O)OC2H4NHSO2C 18 H 37 ; Stearyl (meth)acrylamide, behenyl (meth)acrylamide;

[0112] TIFF2025076414000003.tif2453

[0113] TIFF2025076414000004.tif2253 TIFF2025076414000005.tif2152 TIFF2025076414000006.tif2155

[0114] TIFF2025076414000007.tif2357 TIFF2025076414000008.tif2256 TIFF2025076414000009.tif2156

[0115] TIFF2025076414000010.tif2051 TIFF2025076414000011.tif2054 TIFF2025076414000012.tif2352 TIFF2025076414000013.tif2659

[0116] TIFF2025076414000014.tif2046

[0117] TIFF2025076414000015.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 formula is an acryl compound in which the α-position is a hydrogen atom, but specific examples may be methacryl compounds in which the α-position is a methyl group and α-chloroacryl compounds in which the α-position is a chlorine atom.

[0118] In 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 is preferably 30% by weight or more.

[0119] The polymer of the present disclosure may further include a repeating unit derived from one or more monomers selected from the following monomers (3) to (8):

[0120] (3) Hydrophilic group-containing monomer The polymer of the present disclosure may contain a hydrophilic group-containing monomer (3). 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), particularly an oxyethylene group. In particular, the monomer (3) is preferably an oxyalkylene (meth)acrylate, for example, a polyalkylene (or monoalkylene) glycol mono(meth)acrylate and / or a polyalkylene (or monoalkylene) glycol di(meth)acrylate, or a polyalkylene (or monoalkylene) glycol mono(meth)acrylamide.

[0121] Monomer (3) is formula: CH2=CX b C(=O)-Y b -(R b O) n -A b [In the formula, X bis 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)-Yes, n is an integer from 1 to 90. It is preferable that the oxyalkylene (meth)acrylate is represented by the following formula:

[0122] An example of the monomer (3) is a monomer represented by 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 each independently represents 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 between 1 and 90 It is.] It is preferable that the formula is represented by the following formula:

[0123] n may be, for example, 1 to 50, particularly 1 to 30, and especially 1 to 15 or 2 to 15. Alternatively, n may be, for example, 1. Rb may be a linear or branched alkylene group, for example of the formula -(CH2) x -or-(CH2) x1 -(CH(CH3)) x2 -[In the formula, x1 and x2 are 0 to 6, for example, 2 to 5, and the sum of x1 and x2 is 1 to 6. -(CH2) x1 - and - (CH(CH3)) x2 The order of - is not limited to the depicted formula and may be random. -(R b O) n In -, R may be two or more types (for example, two to four types, particularly two types), and -(R b O) n - is, for example, -(R 1 O) n1 -and-(R 2 O) n2 -[wherein, R 1 and R 2 are different from each other and are alkylene groups having 2 to 6 carbon atoms, n1 and n2 are numbers of 1 or more, and the sum of n1 and n2 is 2 to 90.

[0124] R in formulas (b1), (b2) and (b3) b In particular, R is preferably an ethylene group, a propylene group or a butylene group, and more preferably a butylene group. b R may be a combination of two or more alkylene groups. In that case, it is preferable that at least one of R is an ethylene group, a propylene group, or a butylene group. b Examples of the combination include an ethylene group / propylene group combination, an ethylene group / butylene group combination, and a propylene group / butylene group combination. The monomer (3) may be a mixture of two or more kinds. In that case, at least one of the monomers (3) is a mixture of R bis preferably an ethylene group, a propylene group, or a butylene group. In addition, when using a polyalkylene glycol di(meth)acrylate represented by formula (b2), it is not preferable to use it alone as the monomer (3), but it is preferable to use it in combination with the monomer (b1). In that case, it is also preferable to keep the compound represented by formula (b2) to less than 30% by weight of the monomer (3) used.

[0125] Specific examples of the monomer (3) include, but are not limited to, the following: CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)OH CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H CH2=CHCOO-CH2CH2CH(CH3)OH CH2=CHCOO-CH2CH(CH3)CH2O-H CH2=CHCOO-CH(CH3)CH2CH2O-H CH2=CHCOO-CH2CH(CH2CH3)OH CH2=CHCOO-CH2C(CH3)2O-H CH2=CHCOO-CH(CH2CH3)CH2O-H CH2=CHCOO-C(CH3)2CH2O-H CH2=CHCOO-CH(CH3)CH(CH3)OH CH2=CHCOO-C(CH3)(CH2CH3)OH CH2=CHCOO-(CH2CH2O)2-H CH2=CHCOO-(CH2CH2O)4-H CH2=CHCOO-(CH2CH2O)5-H CH2=CHCOO-(CH2CH2O)6-H CH2=CHCOO-(CH2CH2O)5-CH3 CH2=CHCOO-(CH2CH2O)9-CH3 CH2=CHCOO-(CH2CH2O) 23 -CH3 CH2=CHCOO-(CH2CH2O) 90 -CH3

[0126] 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

[0127] 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

[0128] 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

[0129] CH2=CH-C(=O)-NH-CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH3)OH CH2=CH-C(=O)-NH-CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH(CH3)OH CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH2CH3)OH CH2=CH-C(=O)-NH-CH2C(CH3)2O-H CH2=CH-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=CH-C(=O)-NH-C(CH3)2CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=CH-C(=O)-NH-(CH2CH2O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)4-H CH2=CH-C(=O)-NH-(CH2CH2O)5-H CH2=CH-C(=O)-NH-(CH2CH2O)6-H CH2=CH-C(=O)-NH-(CH2CH2O)9-H CH2=CH-C(=O)-NH-(CH2CH2O)5-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 90 -CH3

[0130] 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

[0131] CH2=C(CH3)-C(=O)-NH-CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-CH2C(CH3)2O-H CH2=C(CH3)-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-C(CH3)2CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-(CH2CH2O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)4-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 90 -CH3

[0132] 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

[0133] The monomer (3) is X 2 is a hydrogen atom. The monomer (3) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

[0134] (4) Monomers containing ion donor groups The polymer of the present disclosure may contain an ion-donating group-containing monomer (4). The monomer (4) is preferably a monomer (particularly, an acrylic monomer) containing an olefinic carbon-carbon double bond and an ion-donating group. The ion-donating group is an anion-donating group and / or a cation-donating group.

[0135] Examples of monomers having an anion donating group include monomers having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.Specific examples of monomers having an anion donating group include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylate phosphate, vinylbenzenesulfonic acid, acrylamido tertiary butylsulfonic acid, and the like, or salts thereof.

[0136] Salts of anion-donating groups include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salts, ethanolammonium salts, triethanolammonium salts, and the like.

[0137] In the monomer having a cation donor group, examples of the cation donor 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 preferably the same or different and are an aliphatic group (particularly an alkyl group) having 1 to 5 carbon atoms, an aromatic group (aryl group) having 6 to 20 carbon atoms, or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example, a benzyl group (C6H5-CH2-)). In the quaternary amino group, the three groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group (particularly an alkyl group) having 1 to 5 carbon atoms, an aromatic group (aryl group) having 6 to 20 carbon atoms, or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example, a benzyl group (C6H5-CH2-)). In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cation donor group may be in the form of a salt.

[0138] The cation donor 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 (particularly, monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and salts thereof are preferred.

[0139] Specific examples of monomers having a cation donor group are as follows. CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g. acetate salts) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br - CH2=C(CH3)COO-CH2CH2-N + (CH3)3I - CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3 CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0140] The ion-donor group-containing monomer (4) is preferably methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate, and more preferably methacrylic acid or dimethylaminoethyl methacrylate.

[0141] (5) Halogenated olefin monomers 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 having 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, and vinylidene halides, such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred because it enhances water repellency (particularly durability of water repellency). The presence of a repeating unit derived from a halogenated olefin monomer (5) enhances the washing durability of the polymer of the present disclosure.

[0142] (6) Crosslinking monomer The polymer of the present disclosure may have a crosslinkable monomer (6). 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 fluorine atoms. It may be a compound that does not contain fluorine atoms. The crosslinkable monomer (6) may be a compound that has at least two ethylenically unsaturated double bonds (preferably (meth)acrylate groups), or a compound that has at least one ethylenically unsaturated double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, and the like.

[0143] The crosslinking monomer may be a mono(meth)acrylate, di(meth)acrylate or di(meth)acrylamide having a reactive group.

[0144] One example of a crosslinkable monomer is a vinyl monomer having a reactive group.

[0145] Examples of crosslinkable monomers include, but are not limited to, diacetone (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0146] (7) Monomers containing cyclic hydrocarbon groups The polymer of this article may have a repeating unit derived from a cyclic hydrocarbon group-containing monomer (7). The cyclic hydrocarbon group-containing monomer (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.

[0147] The cyclic hydrocarbon group-containing monomer (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.

[0148] The cyclic hydrocarbon group may be alicyclic or aromatic, preferably alicyclic. The cyclic hydrocarbon group may be saturated or unsaturated, preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, preferably a bridged ring group. The cyclic hydrocarbon group may have a chain group (e.g., a straight-chain or branched-chain hydrocarbon group).

[0149] The cyclic hydrocarbon group may have 4 or more, 6 or more, or 8 or more carbon atoms, and may have 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less carbon atoms.

[0150] Specific examples of cyclic hydrocarbon groups include cyclohexyl, t-butylcyclohexyl, adamantyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, bornyl, isobornyl, norbornyl, dicyclopentanyl, dicyclopentenyl, benzyl, phenyl, naphthyl, 2-t-butylphenyl, residues in which one or more hydrogen atoms have been removed from these groups (e.g., cyclohexylene, adamantylene, phenylene, naphthylene, etc.), and groups which are substitution products thereof.

[0151] 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, and compounds in which these acrylates are substituted with acrylamide, etc. These may be used alone or in combination of two or more.

[0152] (8) Other monomers The other monomers are not limited to these examples and include acrylonitrile, organosiloxane-containing (meth)acrylates, short-chain alkyl (meth)acrylates, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, vinyl alkyl ethers, etc. The other monomers (8) may be used alone or in combination of two or more.

[0153] <Polymer composition> The combination of monomers (1) to (8) constituting the repeating units of the polymer is not particularly limited as long as it contains (1), and examples are 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) Further, the above combination may be used in combination with another monomer (8). In the case of textile products, it is preferable to use the monomer (1) and the monomer (2) in combination.

[0154] [(1) Amount of monomer] The amount of the repeating units derived from monomer (1) may be 0.1% by weight or more, 0.5% by weight 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 repeat units 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.

[0155] The amount of the repeating unit derived from the monomer (1) may be 100% by weight based on the polymer. In other words, the polymer of the present disclosure may be a polymer of the monomer (1). [(2) Amount of hydrophobic monomer]

[0156] The amount of the repeating units derived from monomer (2) may be 1 weight % or more, 5 weight % or more, 10 weight % or more, 20 weight % or more, 30 weight % or more, 40 weight % or more, 50 weight % or more, 60 weight % or more, 70 weight % or more, 80 weight % or more, or 90 weight % or more, based on the polymer. The amount of repeat units derived from 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 units derived from monomer (2) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, based on 100 parts by weight of the repeating units derived from monomer (1). The amount of the repeating units derived from 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, relative to 100 parts by weight of the repeating units derived from monomer (1). The weight ratio of monomer unit (1) in the polymer, represented by monomer unit (1) / monomer unit (2), 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 monomer unit (1) in the polymer, represented by monomer unit (1) / monomer unit (2), 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.

[0157] In one embodiment, the amount of repeat units derived from monomer (2) may be less than the amount of repeat units derived from monomer (1).

[0158] [(3) Amount of hydrophilic group-containing monomer] The amount of the repeating units derived from monomer (3) may be 1 weight % or more, 5 weight % or more, 10 weight % or more, 20 weight % or more, 30 weight % or more, 40 weight % or more, 50 weight % or more, 60 weight % or more, 70 weight % or more, 80 weight % or more, or 90 weight % or more, based on the polymer. The amount of repeat units derived from 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 units derived from 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, based on 100 parts by weight of the repeating units derived from monomer (1). The amount of the repeating units derived from 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, relative to 100 parts by weight of the repeating units derived from monomer (1).

[0159] [(4) Amount of ion donor group-containing monomer] The amount of the repeating units derived from monomer (4) may be 1 weight % or more, 5 weight % or more, 10 weight % or more, 20 weight % or more, 30 weight % or more, 40 weight % or more, 50 weight % or more, 60 weight % or more, 70 weight % or more, 80 weight % or more, or 90 weight % or more, based on the polymer. The amount of repeat units derived from 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 units derived from monomer (4) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, based on 100 parts by weight of the repeating units derived from monomer (1). The amount of the repeating units 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, relative to 100 parts by weight of the repeating units derived from monomer (1).

[0160] [(5) Amount of halogenated olefin monomer] The amount of repeating units derived from monomer (5) may be 1 weight % or more, 5 weight % or more, 10 weight % or more, 20 weight % or more, 30 weight % or more, 40 weight % or more, 50 weight % or more, 60 weight % or more, 70 weight % or more, 80 weight % or more, or 90 weight % or more, based on the polymer. The amount of repeat units 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, based on the polymer. The amount of the repeating units derived from monomer (5) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, based on 100 parts by weight of the repeating units derived from monomer (1). The amount of the repeating units derived from 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, relative to 100 parts by weight of the repeating units derived from monomer (1).

[0161] [(6) Amount of crosslinkable monomer] The amount of repeating units derived from monomer (6) may be 1 weight % or more, 5 weight % or more, 10 weight % or more, 20 weight % or more, 30 weight % or more, 40 weight % or more, 50 weight % or more, 60 weight % or more, 70 weight % or more, 80 weight % or more, or 90 weight % or more, based on the polymer. The amount of repeat units derived from 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, based on the polymer. The amount of the repeating units derived from monomer (6) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, based on 100 parts by weight of the repeating units derived from monomer (1). The amount of the repeating units derived from 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, relative to 100 parts by weight of the repeating units derived from monomer (1).

[0162] [(7) Amount of Cyclic Hydrocarbon Group-Containing Monomer] The amount of repeating units derived from monomer (7) may be 1 weight % or more, 5 weight % or more, 10 weight % or more, 20 weight % or more, 30 weight % or more, 40 weight % or more, 50 weight % or more, 60 weight % or more, 70 weight % or more, 80 weight % or more, or 90 weight % or more, based on the polymer. The amount of repeat units derived from 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 units derived from monomer (7) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, based on 100 parts by weight of the repeating units derived from monomer (1). The amount of the repeating units derived from 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, relative to 100 parts by weight of the repeating units derived from monomer (1).

[0163] [(8) Amount of other monomers] The amount of repeating units derived from monomer (8) may be 1 weight % or more, 5 weight % or more, 10 weight % or more, 20 weight % or more, 30 weight % or more, 40 weight % or more, 50 weight % or more, 60 weight % or more, 70 weight % or more, 80 weight % or more, or 90 weight % or more, based on the polymer. The amount of repeat units derived from 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 units derived from monomer (8) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, based on 100 parts by weight of the repeating units derived from monomer (1). The amount of the repeating units derived from 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, relative to 100 parts by weight of the repeating units derived from monomer (1).

[0164] <Method of Producing Polymer> The polymer of the present disclosure can be produced by any of the usual polymerization methods, and the polymerization reaction conditions can be selected arbitrarily. Such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

[0165] In solution polymerization, a method is adopted in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, the mixture is heated and stirred at a temperature in the range of 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, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, based on 100 parts by weight of the monomer.

[0166] The organic solvent is inert to the monomers and dissolves them, and may be, for example, an ester (e.g., an ester having 2 to 30 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 30 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol). 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, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total of the monomers.

[0167] In emulsion polymerization, a method is adopted in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, the monomer is polymerized by stirring at a temperature 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, and ammonium persulfate, and oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight relative to 100 parts by weight of the monomer.

[0168] In order to obtain a polymer aqueous dispersion having excellent shelf stability, it is desirable to polymerize the monomer by dispersing it in water into fine particles using an emulsifier capable of applying strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. In addition, various emulsifiers such as anionic, cationic or nonionic emulsifiers can be used as the emulsifier, and are used in the range of 0.5 to 20 parts by weight per 100 parts by weight of the monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible with each other, it is preferable to add a compatibilizer that can sufficiently make these monomers compatible with each other, such as a water-soluble organic solvent or a low molecular weight monomer. The addition of a compatibilizer can improve emulsifiability and copolymerizability.

[0169] Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol, which may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of water. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate, which may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of the total amount of the monomers.

[0170] In the polymerization, a chain transfer agent may be used. The molecular weight of the polymer can be changed depending on the amount of the chain transfer agent used. Examples of the chain transfer agent include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. 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.

[0171] It is preferable to produce the polymer by emulsion polymerization or solution polymerization. After producing the polymer 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 producing the polymer by polymerization. For example, after polymerizing the monomer in the presence of an organic solvent to produce a polymer, water may be added to the polymer mixture, the organic solvent may be distilled off, and the polymer may be dispersed in water. The organic solvent does not have to be distilled off. A surfactant may be added before or after polymerization, or may not be added. Even when a surfactant is not added, a good aqueous dispersion can be obtained.

[0172] <Composition> The composition of the present disclosure includes the polymer of the present disclosure. The composition of the present disclosure can be obtained by combining the polymer of the present disclosure with an additional component (e.g., an emulsifier, a liquid medium, a wax, etc.). The composition of the present disclosure can be obtained by polymerizing the monomer (1), or the monomer (1) and the hydrophobic monomer (2), in the presence of the additional component of the present disclosure (e.g., a surfactant, a liquid medium, a wax, etc.).

[0173] The composition can be an emulsion composition by including the polymer of the present disclosure, an emulsifier, and water.

[0174] [Surfactants] The composition of the present disclosure may include a surfactant as an additional component. In the composition, the surfactant may include a nonionic surfactant. Furthermore, the surfactant may include one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant.

[0175] (Nonionic surfactant) Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides.

[0176] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0177] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a monohydric to hexahydric (particularly dihydric to pentahydric) alcohol (e.g., an aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0178] An example of the ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of the alcohol is a monohydric to hexahydric (particularly dihydric to pentahydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0179] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamine. An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0180] The polyhydric alcohol may be a dihydric to pentahydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (eg, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0181] The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably 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.

[0182] 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. Moreover, the nonionic surfactant preferably has a structure that does not contain an aromatic group in view of environmental issues (biodegradability, environmental hormones, etc.).

[0183] The nonionic surfactant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or acyl group having 2 to 22 carbon atoms, R 2 each is independently the same or different and is an alkylene group having 3 or more carbon atoms (e.g., 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 equal to or greater than 2, q is a number equal to or greater than 0. The compound may be represented by the formula:

[0184] R1 R preferably has 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms. 1 Preferred specific examples include a lauryl group, a tridecyl group, and an oleyl group. R 2 Examples are 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, and a styrene chain, and among these, an oxypropylene chain is preferred.

[0185] Specific examples of nonionic surfactants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C 12 -C 16 ) Thiol, Sorbitan Mono Fatty Acid (C7-C 19 ) or alkyl(C 12 -C 18 ) amines and the like.

[0186] The proportion of the polyoxyethylene block may 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-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. An example of a compound having an HLB of less than 15 is a sorbitan fatty acid ester. An example of a compound having an HLB of 15 or more is a polyoxyethylene alkyl ether. 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 90:10 to 20:80, for example 85:15 to 55:45. The nonionic surfactant may be used alone or in combination of two or more kinds.

[0187] (Cationic Surfactant) The cationic surfactant is preferably a compound having no amide group.

[0188] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene adduct ammonium salt.Specific examples of the cationic surfactant include, but are not limited to, amine salt surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc., alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, pyridinium salts, alkyl isoquinolinium salts, and quaternary ammonium salt surfactants such as benzethonium chloride.

[0189] 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 is a hydrocarbon group having 1 to 40 carbon atoms, X is an anionic group. It is a compound of the formula: R 21 , R 22 , R 23and -R 24 Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0190] The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula: R 1 p - N + R 2 q X - [In the formula, R 1 is C12 or higher (e.g. C 12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50); (CH3, C2H5 are particularly preferred), X is a halogen atom (for example), a C1-C4 fatty acid base, p is 1 or 2, q is 2 or 3, and p+q=4. R 1 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0191] Specific examples of cationic surfactants 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.

[0192] (anionic surfactant) Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic fatty acid salts, N-acylamino acid type surfactants, phosphoric acid mono- or diester type surfactants, and sulfosuccinic acid esters.

[0193] (Amphoteric surfactant) Examples of amphoteric surfactants include alanines, imidazolinium betaines, amido betaines, and betaine acetate. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetate betaine, and fatty acid amidopropyl dimethylamino acetate betaine.

[0194] The surfactant may be a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant, each of which may be one type or a combination of two or more types.

[0195] (amount of surfactant) The amount of the surfactant may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative 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, relative to 100 parts by weight of the polymer.

[0196] The surfactants exemplified in the present disclosure can also be used as emulsifiers. That is, the nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants exemplified in the present disclosure can be used as nonionic emulsifiers, cationic emulsifiers, anionic emulsifiers, and amphoteric emulsifiers.

[0197] [Liquid medium] The composition of the present disclosure may include 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, the liquid medium is a mixture of water and an organic solvent.

[0198] Examples of the organic solvent include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha, kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxyl group (e.g., polyhydric alcohols such as alcohols, glycol-based solvents, ethers of polyhydric alcohols (e.g., monoethers), etc.). These may be used alone or in combination of two or more.

[0199] (amount of liquid medium) The amount of the liquid medium may be 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more, or 97% or more by weight of the composition. The amount of the liquid medium may be 99.9% or less, 99% or less, 95% or less, 90% or less, 80% or less, 70% or less, 60% or less, or 50% or less by weight of the composition.

[0200] The amount of organic solvent may be 0.5% or more, 1% or more, 2% or more, 3% or more, 5% or more, 7.5% or more, 10% or more, 12.5% ​​or more, 15% or more, or 20% or more by weight of the composition. The amount of organic solvent may be 75% or less, 50% or less, 40% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, or 5% or less by weight of the composition.

[0201] 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.

[0202] 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, relative to 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, relative to 100 parts by weight of the polymer.

[0203] 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, based on 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, based on 100 parts by weight of water.

[0204] [silicone] The composition of the present disclosure may contain a silicone in addition to the monomer (1) and the hydrophobic monomer (2).

[0205] Silicones have the formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )2-O-] b -Si(R 53 )3(S1) [In the formula, R 51 each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or an alkoxy group having 1 to 40 carbon atoms; R 53 each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a saturated hydrocarbon group having 1 to 40 carbon atoms; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 5 to 200. The polymer may be represented by the formula:

[0206] R 51 and R 53 In the above, the alkyl group having 1 to 40 carbon atoms and the aryl group having 6 to 40 carbon atoms may be unsubstituted or substituted. R 51 and R 53Specific examples of R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group; a cyclopentyl group, a cyclohexyl group, a cycloheptyl group; a phenyl group, a tolyl group, a naphthyl group, or a group in which some or all of the hydrogen atoms bonded to these groups have been substituted with a halogen atom, an amino group, a cyano group, or the like. 51 and R 53 is preferably a methyl group or an ethyl group. R 51 and R 53 In the above, the alkoxy group having 1 to 40 carbon atoms may be linear or branched. Examples of the alkoxy group having 1 to 40 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0207] The silicone may have at least one long chain hydrocarbon group. For example, R 51 At least one of R 53 At least one of, or R 51 and R 53 may be a long chain hydrocarbon group, and R 51 At least one of (for example, one of) 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. Here, the hydrocarbon group may be linear or branched, and is preferably an alkyl group. Specific examples of the hydrocarbon group include a hexyl group (6 carbon atoms), an octyl group (8 carbon atoms), a lauryl group (12 carbon atoms), a myristyl group (14 carbon atoms), a stearyl group (18 carbon atoms), a behenyl group (22 carbon atoms), a tricosyl group (23 carbon atoms), a lignoceryl group (tetracosyl group, 24 carbon atoms), a cellotyl group (hexacosyl group, 26 carbon atoms), a monthyl group (octacosyl group, 28 carbon atoms), a melissyl group (triacontane group, 30 carbon atoms), and a dotriacontane group (32 carbon atoms).

[0208] The long-chain hydrocarbon group R51 and R 53 Other than R 51 and R 53 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0209] a is an integer of equal to or greater than 0. In terms of ease of industrial production and availability, a may be equal to or less than 40, equal to or less than 30, or equal to or less than 20, and is preferably equal to or less than 30.

[0210] The sum of a and b is 5 to 200. From the viewpoints of ease of industrial production, availability, and handling, the sum of a and b is preferably 10 to 100, and more preferably 40 to 60. a may be 0 to 150, for example, 1 to 100. The lower limit of b may be 1, 2, or 3, and the upper limit of b may be 150, 10, or 5.

[0211] When a or b is 2 or more, R exists in plural. 51 and R 52 Each of may be the same or different.

[0212] R 51 and R 53 Group (for example, R 51 and R 52 Groups and R 53 It is preferable that 50 mol % or more of the total of the alkyl groups) are methyl groups.

[0213] The order of the repeating units bounded by a or b is not limited to the order shown in the chemical formula, but may be any order, i.e., the silicone may be a random polymer or a block polymer.

[0214] For example, silicones may have 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, R 51 each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a long-chain hydrocarbon group; R 52 each independently represents a long chain hydrocarbon group; R 53 each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a long-chain hydrocarbon group; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 5 to 200. The polymer may be represented by the formula: In formula (S2), R 51 and R 53 may have an alkyl group having 3 to 40 carbon atoms or an unsaturated hydrocarbon group having 6 to 40 carbon atoms (for example, a hydrocarbon group having an aromatic ring), but it is preferable that it does not have these groups.

[0215] Examples of silicones are: [ka] [In the formula, a represents an integer of 0 to 150, b represents an integer from 1 to 150; (a+b) is 5 to 200; and n is an integer from 1 to 36 (preferably, n is a long-chain hydrocarbon group).

[0216] Silicone can be synthesized by a conventional method, for example, by subjecting silicone having a SiH group to a hydrosilylation reaction with an α-olefin.

[0217] Examples of silicones having a SiH group include methylhydrogensilicones having a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methylhydrogensiloxane. Among these, methylhydrogensilicones are preferred because they are easy to produce industrially and obtain. Hydrogensilicones (e.g., methylhydrogensilicones) are polydiorganosiloxanes in which a portion of the side chain is replaced with hydrogen, and the hydrogen atom is directly bonded to a silicon atom. When using hydrogensilicones, a catalyst may be used to improve reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine-based catalysts can be used. As these catalysts, organic acid metal salts are preferred, and as organic acids, fatty acids are preferred. From the viewpoint of excellent handling, zinc stearate or the like can be used. It is preferable to use 10 to 40% of the catalyst relative to the methylhydrogensilicone, since the catalyst is more likely to exert its effect. Two or more of amino-modified, epoxy-modified, carboxy-modified, and methylhydrogensilicones may be mixed. All of them are silicones having reactive groups, and it is preferable that they are silicones having film-forming properties. The term "film-forming ability" refers to the ability of the silicone to form a solid film, rather than an oil or gel film, after it is attached to the fiber surface in an emulsion state.

[0218] α-Olefins are compounds from which long-chain hydrocarbon groups in silicones are derived. Specific examples of α-olefins are 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triacontene, and 1-dotriacontene. The hydrosilylation reaction may be carried out by reacting the above-mentioned silicone having a SiH group with an α-olefin in a stepwise manner or all at once, if necessary in the presence of a catalyst.

[0219] The amounts of the SiH group-containing silicone and the α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent or number average molecular weight of the SiH group-containing silicone, respectively.

[0220] Examples of catalysts used in the hydrosilylation reaction include platinum and palladium compounds, and among these, platinum compounds are preferred, such as platinum(IV) chloride.

[0221] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be appropriately adjusted. The reaction temperature is, for example, 10 to 200° C., and 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 and argon. The reaction proceeds without a solvent, but a solvent may be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0222] (Reactive Silicone) The silicone may include reactive silicone. Examples of reactive silicone include polysiloxanes having reactive groups at the side chain, one end, both ends, or at the side chain and both ends. From the viewpoint of excellent slip resistance and excellent water repellency at the same time, polysiloxanes having reactive groups at the side chain and / or both ends may be used. 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, and hydrogen-modified silicone. 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.

[0223] The amino-modified silicone may have 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 is preferably one having 2 or more carbon atoms. The divalent aromatic group is preferably one having 6 or more carbon atoms. The amino group may be either a primary amino group, a secondary amino group, or a tertiary amino group. Examples of organic groups bonded to an amino group include the following: 2-aminoethyl group, N-methyl-2-aminoethyl group, N,N-dimethyl-2-aminoethyl group, N-ethyl-2-aminoethyl group, N,N-diethyl-2-aminoethyl group, N,N-methylethyl-2-aminoethyl group, 3-aminopropyl group, N-methyl-3-aminopropyl group, N,N-dimethyl-3-aminopropyl group, N-ethyl-3-anopropyl group, N,N-diethyl-3-aminopropyl group, and N,N-methylethyl-3-aminopropyl group. These functional groups may be located on the side chains of the polysiloxane or at the ends.

[0224] The epoxy-modified silicone may have 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. In this case, the bond between the organic group and the epoxy group is usually in the form of a glycidyl ether. Examples of such functional groups include a 3-glycidoxypropyl group and a 2-glycidoxyethyl group. These functional groups may be in the side chain of the polysiloxane or at the end.

[0225] 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 is preferably one having 2 or more carbon atoms. The divalent aromatic group is preferably one having 6 or more carbon atoms. Examples of such functional groups include a 3-carboxypropyl group and a 2-carboxyethyl group. These functional groups may be present in the side chain of the polysiloxane or at the terminal.

[0226] (Silicone resin) The silicone may include a silicone resin. The silicone resin may include RSiO 1 / 2 Unit (M unit), RSiO 3 / 2 Units (T units) and SiO 4 / 2 Silicone resin (3) is a silicone resin consisting of at least one selected from R2SiO 2 / 2 It is preferable that the unit (D unit) is not contained from the viewpoint of exerting the effect of the present invention.

[0227] The silicone resin is preferably in a sol state. Examples of R include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, decyl, cetyl, and stearyl groups, but from the standpoint of stability when the silicone resin (3) is in a sol state, availability of raw materials, and cost, R is preferably a methyl group, and more preferably 90% or more of all R are methyl groups. Note that R may be a combination of different types of groups.

[0228] Silicone resin with R2SiO 2 / 2 If the silicone resin contains D units, the anti-slip properties of the composition may be impaired. Also, if the silicone resin contains only Q units, the water repellency of the composition may be impaired.

[0229] The structure of the silicone resin is exemplified by (i) M units and Q units, (ii) M units, T units and Q units, (iii) M units and T units, (iv) T units and Q units, and (v) silicone resins consisting only of T units, and preferably (i) silicone resins consisting of M units and Q units and (v) silicone resins consisting only of T units. (i) The molar ratio (M / Q) of M units and Q units of the silicone resin consisting of M units and Q units is preferably M / Q=0.6 to 1.3, more preferably M / Q=0.8 to 1.1. Two or more of these silicone resins may be used in combination.

[0230] The silicone resin (3) may also contain a structural unit containing a hydroxyl group bonded to a silicon atom. Specifically, (HO)RSiO 2 / 2 Units and (HO)2RSiO 1 / 2 Units: (HO)SiO 3 / 2 Units: (HO)2SiO 2 / 2 Units: (HO)3SiO 1 / 2 A part of the hydroxyl groups may be an alkoxy group represented by an RO group.

[0231] As described in Japanese Patent No. 3852921, a sol containing a silicone resin can be obtained by a manufacturing method in which organodisiloxane, tetraalkoxysilane, and their partial hydrolysis condensates are uniformly dispersed and polymerized in water containing a surfactant, or by a manufacturing method in which the following silane compound is hydrolyzed in water.

[0232] The production method of hydrolyzing a silane compound in water will be described in detail. As a raw material for production, any silane compound can be used as long as the type of hydrolyzable group is chloro or alkoxy, the compound contains one, three or four hydrolyzable groups, and the compound has an alkyl group that satisfies the above conditions.Specifically, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrichlorosilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrichlorosilane, Trichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrichlorosilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, 2-ethylhexyltrichlorosilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, decyltriethoxysilane, cetyltrichlorosilane, cetyltrimethoxysilane, cetyltriethoxy Silane, stearyl trichlorosilane, stearyl trimethoxysilane, stearyl triethoxysilane, trimethyl chlorosilane, trimethyl methoxysilane, trimethyl ethoxysilane, trimethyl isopropoxysilane, dimethyl ethyl chlorosilane, dimethyl ethyl methoxysilane, dimethyl ethyl ethoxysilane, dimethyl propyl chlorosilane, dimethyl propyl methoxysilane, dimethyl propyl ethoxysilane, dimethyl isopropyl chlorosilane, dimethyl isopropyl methoxysilane, dimethyl isopropyl ethoxysilane, di Usable silane compounds include, but are not limited to, methylhexyl chlorosilane, dimethylhexyl methoxysilane, dimethylhexyl ethoxysilane, dimethyldecyl chlorosilane, dimethyldecyl methoxysilane, dimethyldecyl ethoxysilane, dimethylcetyl chlorosilane, dimethylcetyl methoxysilane, dimethylcetyl ethoxysilane, dimethylstearyl chlorosilane, dimethylstearyl methoxysilane, dimethylstearyl ethoxysilane, and partial hydrolysates thereof.From the viewpoints of operability, ease of distilling off by-products, and ease of obtaining raw materials, it is more preferable to use methoxysilane or ethoxysilane. One or a mixture of two or more of these silane compounds may be used.

[0233] As a method for hydrolyzing a silane compound in water, a commonly known method can be used, such as a method in which the hydrolysis reaction is carried out while dropping the silane compound into water, or a method in which water and the silane compound are mixed together and then the hydrolysis reaction is carried out. A hydrolysis catalyst may be used when carrying out the hydrolysis reaction. As the hydrolysis catalyst, a conventionally known catalyst may be used, and it is preferable to use an acidic or alkaline catalyst. In the case of an acidic catalyst, a solid acid such as hydrogen halide, carboxylic acid, sulfonic acid, acidic or weakly acidic inorganic salt, or ion exchange resin is preferable. In the case of an alkaline catalyst, an alkali metal salt such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or sodium hydrogen carbonate, an alkali metal silanolate such as sodium silanolate or potassium silanolate, an amine such as triethylamine, diethylamine, or aniline, or an aqueous ammonia may be used. The amount of the catalyst to be added is preferably adjusted so that the pH of the aqueous solution is 2 to 7 or 7 to 12. After the reaction is completed, a neutralizing agent for neutralizing the acidic or alkaline catalyst may be added as necessary.

[0234] A surfactant may be added to the aqueous solution in order to disperse the silane compound and the hydrolysis reaction product in water. There is no particular limitation on the surfactant, but 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 alone or in combination of two or more. In addition, surfactants that exhibit acidity or alkalinity can also be used as hydrolysis catalysts. There is no particular limitation on the amount of surfactant added, but it is preferably 1 to 50 parts by weight per 100 parts by weight of the silane compound. If the amount is less than 1 part by weight, the effect of adding the surfactant is not sufficiently obtained, and if the amount is more than 50 parts by weight, the water repellency of the water repellent agent may be impaired.

[0235] 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. Silicone resin can be obtained by subsequently carrying out a neutralization reaction as necessary. In addition, alcohols and neutralized salts produced as by-products in the hydrolysis reaction can be removed by vacuum distillation, filtration, or the like. Various additives can be added to this silicone resin. For example, preservatives, thickeners, and the like can be added depending on the purpose.

[0236] (amount of silicone) The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, based on 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, based on 100 parts by weight of the polymer.

[0237] [wax] The composition of the present disclosure preferably contains a wax in addition to the monomer (1) and the hydrophobic monomer (2). By containing the wax, the composition can have good water repellency. The composition of the present disclosure may contain both the silicone and the wax, or may contain only one of the silicone and the wax.

[0238] Examples of wax include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, animal and vegetable wax, and mineral wax. Paraffin wax is preferred. Specific examples of compounds constituting wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane), and normal alkenes (e.g., 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane). The number of carbon atoms in the compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500, or 300 to 1000. These may be used alone or in combination of two or more.

[0239] 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.

[0240] (amount of wax) The amount of the wax may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, based on 100 parts by weight of the polymer. The amount of the 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.

[0241] [Organic acid] The composition of the present disclosure may contain an organic acid as an additional component. As the organic acid, a known one may be used. As the organic acid, carboxylic acid, sulfonic acid, sulfinic acid, etc. are preferably mentioned, and carboxylic acid is particularly preferable. As the carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc. are mentioned, and formic acid or acetic acid is particularly preferable. In the present disclosure, the organic acid may be used alone or in combination of two or more kinds. For example, formic acid and acetic acid may be used in combination.

[0242] (Amount of organic acid) The amount of the organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, based on 100 parts by weight of the polymer. The amount of the 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 the 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).

[0243] [Hardening agent] The composition may include a curing agent (an active hydrogen reactive compound or an active hydrogen containing compound). The curing agent may be added to the composition after polymerization to obtain a polymer.

[0244] 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.

[0245] 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 include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates.

[0246] Examples of aliphatic polyisocyanates 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, 2,6-diisocyanate, 1,2-dimethylphenyl di ... Aliphatic diisocyanates such as isocyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, etc. These may be used alone or in combination of two or more.

[0247] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0248] Examples of the araliphatic polyisocyanate are araliphatic diisocyanate and araliphatic triisocyanate.Specific examples of the araliphatic polyisocyanate 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.

[0249] 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. These may be used alone or in combination of two or more.

[0250] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdione, uretoimine, isocyanurates, iminooxadiazinedione, etc. These may be used alone or in combination of two or more.

[0251] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable even in an aqueous solution and can be used in the same aqueous solution as the composition.

[0252] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, for example, 130°C or higher, the isocyanate group is regenerated and can easily react with the hydroxyl group. Examples of the blocking agent include phenol-based compounds, lactam-based compounds, aliphatic alcohol-based compounds, and oxime-based compounds. The polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0253] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. The chloromethyl group-containing compound is a compound having a chloromethyl group. An example of the chloromethyl group-containing compound is chloromethyl polystyrene. The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid and (poly)methacrylic acid.

[0254] Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide, and the like. Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0255] (Amount of hardener) The amount of the curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, based on 100 parts by weight of the polymer. The amount of the curing agent may be 50 parts by weight or less, 40 parts by weight or more, based on 100 parts by weight of the polymer.

[0256] [Hydrophilic particles] The composition of the present disclosure may contain hydrophilic particles as an additional component. Here, hydrophilicity refers to the property of particles being easily dispersed in an aqueous solvent without agglomeration. For example, when 1.0% by weight of particle powder and an arbitrary dispersant are added to an aqueous solvent, the mixture is stirred at 700 rpm for 10 minutes using a homomixer, and then allowed to stand for 1 hour, if no precipitation or aggregation of the particles is visually observed, the composition is deemed to have hydrophilicity. In addition, for particle aqueous dispersions that are commercially available in a state in which particles are dispersed in an aqueous solvent, the particles contained therein are deemed to have hydrophilicity.

[0257] 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, etc. The surface of the hydrophilic particles may be subjected to a hydrophilization treatment, but is generally not subjected to a hydrophobic treatment.

[0258] The hydrophilic particles are not particularly limited as long as they have hydrophilicity, and examples thereof include inorganic particles (e.g., inorganic oxide particles) such as alumina, silica, and titania, and organic particles such as latex, acrylic, and nylon. Among these, inorganic particles are preferred because of their ease of handling, and at least one selected from the group consisting of silica and alumina is particularly preferred. Examples of commercially available products include silicon oxide particles such as "Snowtex ST-OYL", "Snowtex ST-AK-L" and "Snowtex ST-AK-YL" (all manufactured by Nissan Chemical Industries Co., Ltd.), titanium oxide particles such as "TA300" and "TA300D" (all manufactured by Fuji Titanium Industry Co., Ltd.), and aluminum oxide particles such as "TM-5D" (manufactured by Taimei Chemical Industry Co., Ltd.). These may be used alone or in combination of two or more.

[0259] (Average primary particle size) The average primary particle diameter 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 diameter 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 is preferably 40 nm or less. By being in the above range, the water repellency can be excellent. The average primary particle diameter can be measured with a microscope (scanning electron microscope or transmission electron microscope). Specifically, an arbitrary position of the fabric is observed from above with an arbitrary magnification using a microscope. Next, when the particle shape is spherical, the diameter is regarded as the particle diameter (particle diameter), and when it is non-spherical, the average value of the longest diameter and the shortest diameter is regarded as the particle diameter (particle diameter). The particle size of all particles present within the field of view is measured, and then the field of view is moved and the particle size is measured again. This process is repeated until the particle size is measured at 10 or more points, and the average value is the average primary particle size.

[0260] (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.

[0261] (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.

[0262] (Amount of hydrophilic particles) The amount of 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 amount of the polymer and the hydrophilic particles. The amount of 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 amount of the polymer and the hydrophilic particles. When the amount of hydrophilic particles is within the above range, the water repellency can be excellent.

[0263] The silicone, wax, hydrophilic particles, liquid medium, dispersant, surfactant, or curing agent described above may be added after the polymer is produced, or the polymer may be produced by polymerizing the monomers of the polymer in the presence of the silicone, wax, hydrophilic particles, liquid medium, dispersant, surfactant, or curing agent described above.

[0264] [Other ingredients] The composition may contain other components in addition to the above components. After the polymer is produced, other components may be added. Examples of other components include water and / or oil repellents, antislip agents, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above ingredients, other ingredients include texture adjusters, fabric softeners, antibacterial agents, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming agents, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrink prevention agents, laundry wrinkle prevention agents, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Chinopearl CBS-X), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, and stain removers. As fiber surface modifiers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc., foam inhibitors, moisture absorption and release properties, etc., can be used to impart silk texture and functions, such as silk protein powder, surface modified products thereof, and emulsified dispersions. Specifically, K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemicals), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos), non-ionic polymer compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units, such as FR627 manufactured by GOO Chemical Industry Co., Ltd. and SRC-1 manufactured by Clariant Japan, and other stain prevention agents can be blended. These may be used alone or in combination of two or more.

[0265] (Antistatic agent) Examples of the antistatic agent include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfates, phosphonates, and phosphates; amphoteric antistatic agents such as alkylbetaines and their derivatives, imidazolines and their derivatives, alanines and their derivatives, nonionic antistatic agents such as aminoalcohols and their derivatives, glycerin and its derivatives, and polyethylene glycols and its derivatives. The antistatic agent may be an ion-conductive polymer obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ion-conductive groups. These may be used alone or in combination of two or more.

[0266] (Preservatives) The preservative can be used mainly to enhance the preservative power and the bactericidal power, and to maintain the preservative property during long-term storage. Examples of the preservative include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol. 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 equal to or more than the lower limit of the above range, the effect of adding the preservative is sufficiently obtained, and when the amount is equal to or less than the upper limit, the storage stability of the composition is good.

[0267] (UV absorber) An ultraviolet absorber is a drug that has an ultraviolet protection effect, and is a component that absorbs ultraviolet light and converts it into infrared light, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, 4-t-butyl-4'-methoxybenzoylmethane, etc.

[0268] (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.

[0269] (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).

[0270] (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.

[0271] (Amount of other ingredients) The amount of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the polymer. The amount of the other components 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, relative to 100 parts by weight of the polymer.

[0272] (amount of polymer) The amount of the polymer in the composition 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, 30% by weight or more. The amount of the polymer in the composition 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. <Use of the composition> Examples of applications of the composition in the present disclosure include use as an external treatment agent (surface treatment agent) or an internal treatment agent, a repellent (water repellent, oil repellent, water and oil repellent, etc., particularly water repellent), an antifouling agent, a dirt release agent, a stripping agent, a release agent (external release agent or internal 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 (water repellent, oil repellent, water and oil repellent, etc., particularly water repellent), an antifouling agent, a dirt release agent, a stripping agent, a release agent (external release agent or internal release agent).

[0273] <Method of producing the composition> The method for producing the composition may include a step of reacting (polymerizing) the monomer (1) in a medium (e.g., a liquid medium) containing the monomer (1) and the additional components listed above (e.g., an emulsifier, a liquid medium, a wax, etc.) to obtain a polymer. Alternatively, the method of making the composition may include a step of adding an additional component (e.g., 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 with a solution or dispersion of the additional component (e.g., an emulsifier, a liquid medium, a wax, etc.).

[0274] 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 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 subjecting the composition to ultrasonic waves. There is no particular limitation on the ultrasonic generator, but an output of 500 W or more, for example, 500 to 2000 W, is preferred in terms of efficient mixing. The ultrasonic treatment time may be 0.5 to 60 minutes. For example, a homogeneous composition can be obtained by treating with a 500 W ultrasonic generator for 10 minutes.

[0275] Examples of polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0276] In solution polymerization, a method is adopted in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, relative to 100 parts by weight of the monomer.

[0277] The organic solvent is inactive to the monomers and dissolves them, and may be, for example, an ester (e.g., an ester having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like. The organic solvent is used in an amount of 10 to 3000 parts by weight, for example, 50 to 2000 parts by weight, based on 100 parts by weight of the total of the monomers.

[0278] In emulsion polymerization, a method is adopted in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, the monomer is polymerized by stirring at a temperature in the range of 50 to 80°C for 1 to 20 hours. As the polymerization initiator, water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, and oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight relative to 100 parts by weight of the monomer.

[0279] In order to obtain a polymer aqueous dispersion having excellent shelf stability, it is desirable to polymerize the monomer by dispersing it in water into fine particles using an emulsifier capable of applying 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 are used in the range of 0.5 to 20 parts by weight per 100 parts by weight of the monomer. It is preferable to use an anionic and / or nonionic and / or cationic emulsifier. When the monomers are not completely compatible with each other, it is preferable to add a compatibilizer that can sufficiently make these monomers compatible, such as a water-soluble organic solvent or a low molecular weight monomer. The addition of a compatibilizer can improve emulsifiability and copolymerizability.

[0280] The water-soluble organic solvent may be the organic solvent described above. For example, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc. may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, based on 100 parts by weight of water. In addition, the low molecular weight monomer may be methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., may be used in an amount 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.

[0281] In the polymerization, a chain transfer agent may be used. The molecular weight of the polymer can be changed depending on the amount of the chain transfer agent used. Examples of the chain transfer agent include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of 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.

[0282] The composition may be in the form of a solution, an emulsion (especially an aqueous dispersion), or an aerosol.

[0283] <Water repellent> The water repellent of the present disclosure includes the polymer of the present disclosure. The water repellent of the present disclosure may be the composition of the present disclosure. That is, the composition of the present disclosure can be used as it is as a water repellent. The water repellent 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.

[0284] The water repellent in the present disclosure may not contain any of the compounds selected from the group consisting of compounds having a fluoroalkyl group having 8 or more carbon atoms, compounds having a perfluoroalkyl group having 8 or more carbon atoms, compounds having a fluoroalkyl group having 4 or more carbon atoms, compounds having a perfluoroalkyl group having 4 or more carbon atoms, compounds having a perfluoroalkyl group, compounds having a fluoroalkyl group, and compounds having a fluorine atom. The water repellent in the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0285] <Applications of water repellent> Examples of applications of the water repellent in the present disclosure include an external treatment agent (surface treatment agent) or an internal treatment agent, a repellent (a water repellent, an oil repellent, or a water and oil repellent, etc., particularly a water repellent), an antifouling agent, a soil release agent, a stripping agent, a release agent (an external release agent or an internal release agent), and the like.

[0286] <Water repellent manufacturing method> The method for producing the water repellent of the present disclosure is based on the method for producing the composition of the present disclosure.

[0287] <Manufacturing method of treated products> A method of making a treatment product according to the present disclosure includes applying a water repellent according to the present disclosure to a substrate.

[0288] [Processing products] Examples of substrates treated with the water repellent of the present disclosure include fiber substrates, stone materials, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plasters. Examples of fiber products include various types of natural fibers from animals and plants, 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 mixtures of these fibers. As an example of a substrate to be treated with a water repellent, an example of a woven or knitted fabric will be described in detail.

[0289] (Woven and knitted fabrics) ·Method of manufacturing knitted fabrics The woven or knitted fabric can be obtained by weaving and knitting the long and short fiber yarns made of the above-mentioned fibers to obtain a green fabric, which is then post-processed and water-repellent treated. The weaving and knitting can be performed using a known weaving machine or knitting machine, and the preparation process prior to the weaving and knitting can also be performed using known equipment.

[0290] The woven or knitted fabric can be post-processed using known scouring and dyeing methods and equipment suitable for the fiber material of the woven or knitted fabric.

[0291] After the post-processing, the woven or knitted fabric may be subjected to a water-repellent treatment. In the water-repellent treatment, first, an aqueous solution containing a water repellent (which may be the water repellent or composition in the present disclosure) is prepared. Next, the aqueous solution is applied to the woven or knitted fabric after the post-processing based on a padding method, a spray method, a kiss roll coater method, a slit coater method, or the like, and then dried and then subjected to a dry heat treatment. The aqueous solution may also contain a crosslinking agent, a softener, an antistatic agent, or the like as necessary. After the water-repellent treatment, the woven or knitted fabric may be calendered to further improve the water-repellent performance.

[0292] The woven and knitted fabrics are suitable for use in clothing applications requiring water repellency, particularly in sportswear applications for outdoor activities, skiing, snowboarding, golf, etc., and uniform applications.

[0293] Laminated fabric The woven or knitted fabric of the present disclosure may be provided as a laminated fabric having a moisture-permeable waterproof layer on one side thereof. The moisture-permeable waterproof layer may be laminated directly onto the woven or knitted fabric, or may be laminated onto the woven or knitted fabric via an adhesive layer. When the laminated fabric of the present disclosure is used for clothing applications, the woven or knitted fabric side is disposed on the side that repels rainwater, etc.

[0294] Breathable waterproof layer The moisture-permeable waterproof layer is a layer that covers one side of the woven or knitted fabric, and is a layer formed of a resin or a membrane structure that has waterproof and moisture-permeable properties.

[0295] The moisture-permeable waterproof layer may be formed by applying a resin (a resin that constitutes the moisture-permeable waterproof layer) directly to the woven or knitted fabric, or may be laminated to one side of the woven or knitted fabric via an adhesive layer described below.

[0296] The resin constituting the moisture permeable waterproof layer is not particularly limited, but may be: Non-porous and porous resins are used. For non-porous ones, polyurethane resins and polyester elastomer resins that have hydrophilic components are used to provide moisture permeability. For porous ones, polyurethane resins that form wet-type porous membranes and polyurethane resins that are made porous by electrospinning are used, as well as PTFE porous membranes and PE or PP porous membranes.

[0297] As the polyurethane resin, a conventionally known resin obtained by reacting a polyisocyanate component with a polyol component can be used.

[0298] The moisture-permeable waterproof film having a microporous structure can be obtained by subjecting a DMF solution of a polyurethane resin containing inorganic fine powder to a wet coagulation method. Examples of the inorganic fine powder include fine powders made of silicon dioxide, aluminum dioxide, titanium dioxide, and the like. The average primary particle size 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 weight of the moisture-permeable waterproof layer.

[0299] The moisture-permeable waterproof layer preferably has a thickness of 5 μm or more, and more preferably 10 to 30 μm. When the thickness is in the above range, the waterproof property and moisture permeability are well balanced, and further, there is an advantage in terms of texture.

[0300] ·Adhesive layer The laminated fabric preferably includes an adhesive layer. In other words, the woven or knitted fabric and the moisture-permeable waterproof layer are preferably laminated via an adhesive layer. In addition, it is preferable that the adhesive layer is a discontinuous layer such as a dot or lattice pattern in terms of moisture permeability.

[0301] The type of adhesive constituting the adhesive layer is not particularly limited, but it is preferable that the adhesive has excellent compatibility with the moisture-permeable waterproof layer. For example, when a resin mainly composed of polyurethane resin is selected as the resin constituting the moisture-permeable waterproof layer, it is preferable to adopt an adhesive layer made of a polyurethane-based adhesive. The polyurethane-based adhesive may be of any structure such as ether-based, ester-based, or polycarbonate-based.

[0302] The adhesive layer may be formed over the entire surface of one side of the woven or knitted fabric, or may be formed in a pattern from the viewpoint of moisture permeability, texture, etc. The shape of the pattern is not particularly limited, but examples include dots, lines, a lattice, a checkered pattern, a tortoiseshell pattern, etc., and it is preferable that any of these patterns are uniformly arranged over the entire surface.

[0303] The thickness of the adhesive layer is preferably about 10 to 100 μm, and more preferably 20 to 80 μm.

[0304] · Lining fabric In the laminated fabric of the present disclosure, a lining fiber fabric may be laminated on the moisture-permeable waterproof layer (on the side of the moisture-permeable waterproof layer opposite to the side on which the woven or knitted fabric of the present disclosure is laminated). The lining fiber fabric can protect the moisture-permeable waterproof layer and can provide even better waterproofness (water pressure resistance) and strength.

[0305] Examples of the fiber fabric for the lining include various woven fabrics and knitted fabrics. Among them, knitted fabrics are preferred because the constituent yarns are more likely to protrude from the surface than woven fabrics, the surface is not flat, and the anchor effect is more pronounced, making it less likely to peel off from the moisture-permeable waterproof layer. In addition, tricot knitted fabrics are preferred because they can obtain a long grey fabric during knitting, have fewer seams, and can be evenly layered on the moisture-permeable waterproof layer.

[0306] The material of the fiber constituting the lining fiber fabric is not particularly limited and can be selected as appropriate, but nylon fiber is preferable. This is because acid dyes are generally used in nylon fibers, and migration and sublimation of disperse dyes to the moisture-permeable waterproof layer, which is a problem in polyester fibers and the like that use disperse dyes, is unlikely to occur. The form (long fiber, short fiber, or spun yarn) or fineness of the fiber constituting the lining fiber fabric is not particularly limited and can be selected as appropriate within a range that does not impair the effects of the present disclosure.

[0307] Laminated fabric properties The laminated fabric has excellent waterproofness. A suitable example of the waterproofness of the laminated fabric of the present disclosure is a water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method) of, for example, 10,000 mm or more, preferably 15,000 mm or more, more preferably 16,000 mm or more, and particularly preferably 20,000 mm or more.

[0308] The laminated fabric has excellent moisture permeability. A suitable example of the moisture permeability of the laminated fabric of the present disclosure is a moisture permeability measured according to JIS L 1099:2021 B-1 method (potassium acetate method) of, for example, 10,000 g / m 224h or more, preferably 15000g / m 2 24h or more, more preferably 20,000g / m 2 The upper limit of the moisture permeability is not particularly limited, but is, for example, 40,000 g / m 2 24h or 35,000g / m 2 24h mm. In addition, the moisture permeability measured according to JIS L 1099:2021 A-1 method (calcium chloride method) is, for example, 4000 g / m 2 24h or more, preferably 8000g / m 2 24 hours or more, more preferably 10,000 g / m 2 The upper limit of the moisture permeability is 13,000 to 15,000 g / m 2 Approximately 24 hours.

[0309] In the laminated fabric of the present disclosure, the peel strength between the woven or knitted fabric and the moisture-permeable waterproof layer, as measured according to the method of JIS K 6404-2, is preferably, for example, 2.55 N / 2.54 cm or more for clothing applications, and may be preferably 5 N / 2.54 cm or more for use in applications.

[0310] ·Laminated fabric manufacturing method The method for producing the laminated fabric is not particularly limited, and examples thereof include the first and second production methods described below. First manufacturing method: The first manufacturing method includes a step of forming the moisture-permeable waterproof layer by applying a resin that constitutes the moisture-permeable waterproof layer to the surface of a woven or knitted fabric. Second manufacturing method: This method includes a step of forming an adhesive layer on the woven or knitted fabric or the moisture-permeable waterproof layer, and a step of bonding the woven or knitted fabric and the moisture-permeable waterproof layer together via the adhesive layer.

[0311] In the first manufacturing method, the resin constituting the moisture-permeable waterproof layer can be applied to the surface of the woven or knitted fabric by, for example, a coating method. In the coating method, a knife coater or a comma coater can be used. From the viewpoint of providing excellent moisture permeability, it is preferable to obtain the moisture-permeable waterproof layer by a wet method.

[0312] In the second manufacturing method, the method of forming the adhesive layer on the woven or knitted fabric or the moisture-permeable waterproof layer includes, for example, a lamination method. In the lamination method, the adhesive layer can be formed by using a resin solution or a hot melt method. First, a moisture-permeable waterproof layer-forming resin composition (for example, a resin composition containing a resin and an organic solvent) is applied to the surface of a release material (such as release paper, release cloth, or release film) with a clearance, a moisture-permeable waterproof layer is formed while adjusting the thickness, and the film is completely reacted by drying and heat treatment. The release material can be appropriately removed after lamination or aging. In addition, when lamination is performed by a hot melt method, the release material can be peeled off and the film alone can be laminated. In addition, the moisture-permeable waterproof membrane can be made by laminating membranes produced without solvent using extrusion methods such as the T-die method and inflation, porous membranes produced using the electrospinning method, and porous membranes made of PTFE, PE, PP, etc.

[0313] Then, an adhesive layer is formed on the woven or knitted fabric or the moisture-permeable waterproof layer. For example, in the case of a method using a resin solution, a two-component curing polyurethane resin solution adjusted to a viscosity in the range of 500 to 5000 mPa·s may be applied over the entire surface or in a pattern. The adhesive layer is then dried to form an adhesive layer, and the woven or knitted fabric and the moisture-permeable waterproof layer are bonded together via the adhesive layer, and the two are pressure-bonded or thermo-press-bonded to each other, thereby completing the second manufacturing method.

[0314] On the other hand, in the case of hot melt, it is preferable to use a moisture-curing resin that reacts with moisture in the air, and in practical use, it is more preferable to use one that melts at a temperature range of about 80 to 150 ° C. In this case, first, the hot melt resin is melted while taking into consideration the melting point of the resin and the viscosity when melted. Then, the molten resin is applied onto the woven or knitted fabric or the moisture-permeable waterproof layer, and matured 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 the second manufacturing method can be carried out by pressing. Alternatively, when texture is important, the moisture-permeable waterproof film can be applied in a pattern and bonded to the woven or knitted fabric.

[0315] Thereafter, a fiber fabric for the lining can be laminated onto the moisture-permeable waterproof layer using any suitable known method.

[0316] ·Applications of laminated fabric The laminated fabric has excellent water repellency and moisture-permeable waterproof properties, and the moisture-permeable waterproof layer does not peel off even in harsh environments, so it is suitable for use in fields such as uniform clothing, sports clothing, and outdoor products used outdoors.

[0317] [Processing method] The water repellent of the present disclosure can be applied to a substrate (particularly a fiber substrate) as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The water repellent of the present disclosure may be dispersed and diluted in an organic solvent or water as necessary, and attached to the surface of the substrate by a known method such as dip coating, spray coating, foam coating, etc., and then dried. After drying, a fiber product to which the solid components of the water repellent are attached is obtained. If necessary, it may be applied together with a suitable crosslinking agent and cured. Furthermore, it is also possible to use the water repellent of the present disclosure in combination with various additives such as water and / or oil repellents, antislip agents, antistatic agents, texture adjusters, softeners, antibacterial agents, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming assistants, compatibilizers, antifreeze agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, and defoamers. Examples of various additives may be the same as those described in the "other components" of the above-mentioned composition. The concentration of the polymer in the treatment agent to be brought into contact with the substrate may be appropriately changed depending on the application, but may be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

[0318] [Textile products] There are various examples of the fiber substrate as the substrate, such as cloth products and paper products. The fiber product as the substrate is also called the fiber substrate.

[0319] Examples of textile products include natural fibers of animal and vegetable origin such as cotton, hemp, wool, silk, etc., synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc., semi-synthetic fibers such as rayon, acetate, etc., inorganic fibers such as glass fiber, carbon fiber, asbestos fiber, etc., or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics, nonwoven fabrics, clothing-type cloth, and carpets, but the treatment may also be performed on fibers, yarns, and intermediate textile products (e.g., slivers or rovings) in a state prior to being made into cloth.

[0320] Examples of paper products include paper made of bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, waste paper pulp such as recycled newsprint, recycled magazine paper, recycled corrugated cardboard or deinked recycled paper, paper containers, paper molded articles, etc. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium quality paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc.

[0321] The water repellent can be applied to the textile substrate by any of the methods known for treating textile substrates (e.g., fabrics) with liquids. The textile substrate may be immersed in the water repellent, or the solution may be applied or sprayed onto the textile substrate. The treated textile substrate is preferably dried and cured by heating to develop water 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.

[0322] Alternatively, the water repellent may be applied to the textile substrate by a cleaning process, such as by laundering or by a dry cleaning process.

[0323] The treated textile substrate may be a fabric, including woven, knitted and nonwoven fabrics, apparel fabrics and carpets, but may also be a fiber or yarn or intermediate textile product (e.g., sliver or roving, etc.). The water repellent agents of the present disclosure are particularly effective in rendering textile products (e.g., synthetic fibers) water repellent.

[0324] The fibers constituting the fiber 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.

[0325] Examples of natural fibers include cotton, flax, cellulosic fibers such as pulp, chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as ground wood pulp (GP), pressure-risen ground wood pulp (PGW), and thermomechanical pulp (TMP), chemical pulps such as high yield unbleached softwood kraft pulp (HNKP; N material), bleached softwood kraft pulp (NBKP; N material, NB material), unbleached hardwood kraft pulp (LUKP; L material), and bleached hardwood kraft pulp (LBKP, L material), waste paper pulps such as deinking pulp (DIP) and waste pulp (WP), and semi-chemical pulps (CP).

[0326] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymer polyesters; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers are acetate and triacetate. Examples of regenerated fibers are rayon, cupro, polynosic rayon, lyocell, and tencel. Examples of inorganic fibers are glass fiber and carbon fiber.

[0327] Alternatively, the textile substrate may be leather. The manufactured polymer may be applied to the leather from an aqueous solution or emulsion at various stages of the leather processing, for example during the wet processing of the leather or during the finishing of the leather, to render the leather hydrophobic and oleophobic. Alternatively, the fibrous substrate may be paper. The manufacturing polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example during the drying period of the paper.

[0328] "Treatment" means that the water repellent is applied to the substrate by immersion, spraying, coating, etc. The treatment causes the polymer, which is the active ingredient of the water repellent, to penetrate into the substrate and / or to adhere to the substrate surface. In other words, the treatment results in a substrate (e.g., a textile product) to which the polymer in the water repellent of the present disclosure is adhered. Such a substrate is a textile product having water repellency, i.e., a water-repellent textile product.

[0329] [Pretreatment of textile substrates] The textile substrate may be pretreated before being treated with the water repellent of the present disclosure. Pretreatment of the textile substrate may impart excellent fastness to the textile substrate after treatment with the water repellent.

[0330] Examples of pretreatments of fiber substrates include cationization treatment by reaction with a reactive quaternary ammonium salt, anionization treatment such as sulfonation, carboxylation, and phosphation, and acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment.

[0331] The method for pretreating the fiber substrate is not limited, and the fiber substrate can be pretreated by a conventionally known method. The pretreatment liquid may be dispersed and diluted in an organic solvent or water as necessary, and applied to the surface of the 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 may be adjusted depending on the desired degree of treatment. As an example of a method for pretreating the fiber substrate, a method for pretreating the fiber substrate with a hydrocarbon-based water repellent will be described in detail.

[0332] The pretreatment method for the fiber substrate is to add -SO3M to the fiber. 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) (hereinafter, also referred to as a "specific functional group").

[0333] M 1 Examples of M include H, K, Na, and ammonium ion which may have a substituent. 2 Examples of X include H, K, Na, and ammonium ion which may have a substituent. 1 Or X 2 When is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0334] The fibers containing the specific functional groups (hereinafter, sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following method. (i) A compound having the specific functional group is attached to a fiber material. The attachment of the compound may be in a state where a part of the compound is chemically bonded to a part of the fiber to the extent that a sufficient amount of the specific functional group remains. (ii) A fiber is prepared in which the specific functional group is directly introduced into the material constituting the fiber.

[0335] In the case of (i), for example, a functional group-containing fiber can be obtained by a functional group introduction step in which a fiber material is treated with a pretreatment liquid containing one or more compounds having the specific functional group.

[0336] The material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, hemp, silk, wool, etc., semi-synthetic fibers such as rayon, acetate, etc., synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, polypropylene, etc., and composite fibers, blended fibers, etc. The form of the fiber material may be any of fibers (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, paper, etc.

[0337] In this embodiment, from the viewpoint of improving the water repellency of the obtained textile product, it is preferable to use textile materials containing polyamide and polyester as raw materials, and in particular, it is preferable to use nylons such as nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.

[0338] Above - SO3M 1 As the compound having the formula (I), a phenol-based polymer can be used. As such a phenol-based polymer, for example, one containing at least one compound represented by the following general formula can be mentioned.

[0339] [ka] [In formula (2), X 2 Ha-SO3M 3 (In the formula, M 3 represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0340] [ka] [In the formula, M 4 represents a monovalent cation.

[0341] The above M 3 Examples of the cation include H, K, Na, and ammonium ion which may have a substituent.

[0342] The above M 4 Examples of the cation include H, K, Na, and ammonium ion which may have a substituent.

[0343] 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.

[0344] Above - COOM 2 Examples of compounds having the formula include polycarboxylic acid polymers.

[0345] As the polycarboxylic acid polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer, or a commercially available product can be used.

[0346] Examples of the method for producing a polycarboxylic acid polymer include a method in which a radical polymerization initiator is added to an aqueous solution of the above-mentioned monomer and / or its salt, and the mixture is heated and reacted at 30 to 150° C. for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, isopropyl alcohol, or an aqueous solvent such as acetone may be added to the aqueous solution of the above-mentioned monomer and / or its salt. Examples of the radical polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox-based polymerization initiators such as combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo-based polymerization initiators. These radical polymerization initiators may be used alone or in combination of two or more. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added for the purpose of adjusting the degree of polymerization.

[0347] In addition to the above monomers, copolymerizable monomers can be used in the radical polymerization. Examples of the copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. The acrylates and methacrylates are preferably those having a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used alone or in combination of two or more.

[0348] The carboxyl group in the polycarboxylic acid polymer may be free or may be neutralized with an alkali metal, an amine compound, etc. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0349] The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, and more preferably from 3,000 to 15,000, from the viewpoint of improving the water repellency of the resulting textile product.

[0350] As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (product name, manufactured by Nicca Chemical Co., Ltd.) and "Ceropol PC-300" (product name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0351] Above -OP(O)(OX 1 )(OX 2 ) is exemplified by a phosphate ester compound represented by the following general formula: [ka] [where, X 1 Or X 2 is the same as above, and X 3 represents an alkyl group having 1 to 22 carbon atoms.

[0352] As the phosphate ester compound, phosphate monoesters, diesters and triesters, in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

[0353] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0354] As the phosphate ester compound, for example, a commercially available product such as "Phosphanol ML-200" (product name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0355] The pretreatment liquid containing one or more compounds having the specific functional group may be, for example, an aqueous solution of the above-mentioned compounds. The pretreatment liquid may also contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0356] Examples of the method for treating the textile material with the pretreatment liquid include padding, immersion, spraying, and coating. Examples of padding include a method using a padding device described on pages 396-397 of Textile Dyeing and Processing Dictionary (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of Color Dyeing Chemistry III (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating include a method using a coating machine described on pages 473-477 of Dyeing and Finishing Equipment Directory (published by Sen-sha, 1981). Examples of immersion include a method using a batch-type dyeing machine described on pages 196-247 of Dyeing and Finishing Equipment Directory (published by Sen-sha, 1981), and a liquid flow dyeing machine, air flow dyeing machine, drum dyeing machine, winch dyeing machine, washer dyeing machine, cheese dyeing machine, etc. can be used. Examples of the spray treatment include an air spray in which the treatment liquid is sprayed in the form of a mist using compressed air, and a method using an air spray of a liquid pressure atomization type. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be appropriately adjusted in consideration of various conditions such as the purpose and performance. In addition, when the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after it is applied to the fiber material in order to remove the water. There is no particular limit to the drying method, and either a dry heat method or a wet heat method may be used. There is also no particular limit to the drying temperature, and for example, drying may be performed 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.

[0357] When the textile material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as the dyeing. However, when reduction soaping is carried out, there is a risk that the compound having the specific functional group (e.g., a phenolic polymer compound, etc.) adsorbed during the process may fall off, so it is preferable to carry out the treatment after reduction soaping after dyeing.

[0358] The treatment temperature in the immersion treatment can be 60 to 130° C. The treatment time can be 5 to 60 minutes.

[0359] In the functional group introduction step using a pretreatment liquid, the amount of the compound having the specific functional group attached is preferably 1.0 to 7.0 parts by weight per 100 parts by weight of the textile material. Within this range, durable water repellency and texture can be simultaneously achieved at high levels.

[0360] The pretreatment liquid is preferably adjusted to a pH of 3 to 5. The pH can be adjusted using a pH adjuster such as acetic acid or malic acid.

[0361] In the pretreatment solution, a salt may be used in combination in order to effectively adsorb the compound having the specific functional group to the fiber material by the salting-out effect. Examples of the salt that can be used include sodium chloride. Examples of suitable salts include sodium carbonate, ammonium sulfate, and sodium sulfate.

[0362] In the functional group introduction step using the pretreatment liquid, it is preferable to remove the compound having the specific functional group that has been treated in excess. An example of a removal method is washing with water. By removing the compound sufficiently, it is possible to prevent the development of water repellency in the subsequent water repellent treatment from being hindered, and in addition, the feel of the resulting textile product is improved. In addition, it is preferable to thoroughly dry the resulting functional group-containing fiber before contacting it with a hydrocarbon-based water repellent.

[0363] (ii) An example of a fiber in which the specific functional group is directly introduced into the material constituting the fiber is cationic dyeable polyester (CD-PET).

[0364] From the viewpoint of improving the water repellency of the resulting textile product, the functional group-containing fiber preferably has a surface zeta potential of −100 to −0.1 mV, more preferably −50 to −1 mV. The zeta potential of the fiber surface can be measured, for example, by a zeta potential / particle size measuring system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0365] As a method for treating the pulp base material, an internal addition treatment method in which a repellent is added to the pulp (e.g., pulp slurry) before papermaking, or an external addition treatment method in which a repellent is applied to the pulp (e.g., pulp product) after papermaking can be used. Examples of the internal addition treatment method include mixing, immersion, etc., and may include a step of adding a 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. The treatment may be an external addition treatment or an internal addition treatment. For example, when the pulp base material is paper, the paper may be coated with the repellent, or the solution may be attached or sprayed onto the paper, or the paper may be mixed with the pulp slurry before papermaking and treated.

[0366] 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

[0367] Examples of the present disclosure will be specifically described below, but the present disclosure is not limited to these examples.

[0368] <Test Method> The test procedure is as follows.

[0369] [Water repellency] The water repellency of the treated test fabric was evaluated according to the spray method of JIS-L-1092 (AATCC-22). The water repellency was evaluated according to the following criteria, where a higher score indicates better water repellency. 100 No wetting or water droplets were observed on the surface. 90 The surface did not wet, but small water droplets were observed adhering to it. Wetting of small individual water droplets was observed on the surface. 70 Half of the surface showed wetting, with small individual wettings observed penetrating the fabric. 50 Wetting was observed over the entire surface. 0 Wetting was observed over the entire front and back surfaces.

[0370] [Light oil repellency] Polyester and nylon fabrics were immersed in the dispersions of the Examples and Comparative Examples, and then heat-treated at 170°C for 60 seconds for evaluation. An oil made by blending oleic acid / PEG at a ratio of 1:9 was applied to the surface of the treated fabric, and the oil repellency was evaluated on the following four-point scale. Depending on the condition, intermediate values ​​(B+, B-, C+, C-) were assigned. A: The droplets are clear (not wet) and round. B: The edges and bottom of the droplets are slightly dark and rounded. C: Some liquid droplets have soaked into the fabric. D: The droplet is completely saturated.

[0371] [Chalk mark resistance] Each test cloth was placed on a flat surface, the surface of the test cloth was lightly scratched with a fingernail, and the trace of the scratching with the fingernail, which was left like chalk, was visually evaluated. The results are shown in the table. ◎: No trace at all ○: The trail appears faint ◯△: The trail appears faint △: The trajectory is visible ×: The trail appears dark

[0372] Silicon-based monomer (A) The following Si-based monomer (A) was obtained in accordance with JP 2019-89715 A. TIFF2025076414000020.tif56115

[0373] Silicon-based monomer (B) [Preparation of monomer] (Synthesis of intermediate 1) A four-neck flask was equipped with a thermometer, a dropping funnel, and an N2 line, and the flask was immersed in an ice bath. Then, 14.74g (50.5mmol) of 1,1,1,3,3-pentamethyldisiloxane, 0.04g of tris(pentafluorophenyl)borane, 30ml of toluene, and a stirrer were added to the flask and the solution was stirred. Then, N2 was purged from the N2 line for 3 minutes. Then, 5.1ml (23.7mmol) of (3-chloropropyl)diethoxy(methyl)silane and 10ml of toluene were added to the dropping funnel and this solution was slowly added to the flask. After the dropping was completed, the ice bath was removed and stirring was continued at room temperature for about 6 hours. After confirming the Si-OEt conversion by 1-NMR, neutral alumina was added to the flask and stirred for 30 minutes. The alumina mixture after stirring was filtered through a 0.45μm filter to obtain a solution. The solvent was removed from the resulting solution using a rotary evaporator to obtain a transparent liquid, Intermediate 1. The characteristics of Intermediate 1 were evaluated by 1H-NMR and GC. (Synthesis of Si-based monomer (B)) A four-neck flask was equipped with a thermometer, a dropping funnel, and an N2 line, and the flask was immersed in an ice bath. Then, 0.01 g of butylated hydroxytoluene (BHT), 0.36 g of potassium iodide (KI), 0.98 g of sodium acrylate, 40 ml of dimethylformamide (DMF), and 5 g of intermediate 1 were added to the flask, and a stirrer was added to obtain a mixture, and N2 was purged from the N2 line for 3 minutes. Then, the flask was heated to 120°C and the mixture was stirred for 5 hours. After that, the flask was cooled to 50°C and transferred to a separatory funnel. In the separatory funnel, the mixture was washed four times with 20 g of water to obtain a yellow liquid. This was dried with 5 g of sodium sulfate, and the resulting mixture was filtered to obtain Si-based monomer (B) as a transparent liquid. The characteristics of Si-based monomer (B) were evaluated by 1H-NMR and GC. JPEG2025076414000021.jpg59124

[0374] [Preparation of raw materials] (Production Example of Silicone Polymer-Containing Aqueous Dispersion) Manufacturing Example 1 A 500 ml plastic container was charged with 15 g of a water-soluble glycol solvent as an organic solvent, 100 g of pure water and 100 g of a Si-based monomer (A) as a liquid medium, and 4 g of a sorbitan fatty acid ester, 4 g of a cationic emulsifier, and 3 g of a polyoxyethylene alkyl ether as surfactants, and the mixture was heated to 80°C and stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. Next, this mixture was transferred to a 500 ml four-necked separable flask, and after nitrogen replacement, 0.1 g of lauryl mercaptan was charged as a chain transfer agent. Furthermore, 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 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 a silicone polymer with a non-volatile content concentration of 30% (more specifically, an aqueous dispersion containing a silicone polymer, a surfactant, and a liquid medium).

[0375] Manufacturing Example 2 A 500 ml plastic container was charged with 15 g of a water-soluble glycol 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, and 4 g of sorbitan fatty acid ester, 4 g of a cationic emulsifier, and 3 g of polyoxyethylene alkyl ether as surfactants, and the mixture was heated to 80°C and stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. Next, this mixture was transferred to a 500 ml four-necked separable flask, and after nitrogen replacement, 0.1 g of lauryl mercaptan was charged as a chain transfer agent. Furthermore, 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 a silicone polymer with a non-volatile content of 30% (more specifically, an aqueous dispersion containing a silicone polymer, a surfactant, and a liquid medium).

[0376] Manufacturing Examples 3, 4, 9-11 Except for changing the compounding recipe 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.

[0377] Production Example 5 A 500 ml plastic container was charged with 15 g of a water-soluble glycol solvent as an organic solvent, 100 g of pure water as a liquid medium, 30 g of Si-based monomer (A), 56 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, and the mixture was heated to 80°C and stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. The mixture was then transferred to a 500 ml autoclave, and after nitrogen replacement, 0.1 g of lauryl mercaptan and 14 g of vinyl chloride were charged as a chain transfer agent. Furthermore, 0.3 g of an azo group-containing water-soluble initiator was added as a polymerization initiator, and the mixture was heated to 60°C and reacted for 4 hours to obtain an aqueous dispersion of a silicone-acrylic polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a non-volatile concentration of 30%.

[0378] Manufacturing Examples 6-8 Except for changing the compounding recipe 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.

[0379] Comparative manufacturing examples 1-2 Comparative aqueous dispersions were prepared in the same manner as in Production Example 1, except that the blending recipe was changed according to Table 1.

[0380] [Table 1] The numbers in the table are the amounts (g)

[0381] Example 1 The aqueous dispersion with a non-volatile content of 30% prepared in Production Example 1 was diluted with tap water to prepare a treatment solution with a non-volatile content of 1.5%. Polyester cloth, nylon cloth, and polyester / spandex cloth were immersed in this treatment solution and then squeezed with a mangle. The treated cloth was passed through a pin tenter at 170°C for 1 minute, dried, and cured. The test cloth thus treated was evaluated for water repellency, light oil repellency, and chalk mark resistance as described above. The evaluation results are shown in Table 2.

[0382] Examples 2 to 11 A treatment solution with a non-volatile content of 1.5% was prepared in the same manner as in Example 1, except that the compounding recipe was changed according to Table 2. This treatment solution was used to treat fabric in the same manner as in Example 1, and the water repellency, light oil repellency, and chalk mark resistance were evaluated. The results are shown in Table 2.

[0383] Comparative Examples 1-2 A treatment solution with a non-volatile content of 1.5% was prepared in the same manner as in Example 1, except that the compounding recipe was changed according to Table 2. This treatment solution was used to treat fabric in the same manner as in Example 1, and the water repellency, light oil repellency, and chalk mark resistance were evaluated. The results are shown in Table 2.

[0384] [Table 2] [Industrial Applicability]

[0385] The polymers of the present disclosure can be utilized to impart water and oil repellency to a variety of products (e.g., paper, textiles, etc.).

Claims

1. A polymer for a water repellent agent, the polymer having the following formula: CR ａ R ｂ =C(-R ｃ )-X-SiY ３－ｎ Z ｎ [In the 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; Each Y is independently a hydrocarbon group having 1 to 10 carbon atoms; n is an integer of 1 or 2, Each Z is independently ____]] １ ２ ) ｐ () ２ ) ｑ  ２ __) (__)] ３ ３ ) ２ : ４ であり、 Z １ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ １１ ３ and Z １１ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ １１１ ３ and Z １１１ are each independently a hydrocarbon group having 1 to 10 carbon atoms, Z ２ is -O- or -CH ２ - and Z ３ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ ３１ ３ and Z ３１ are each independently a hydrocarbon group having 1 to 10 carbon atoms, Z ４ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or -OSiZ ４１ ３ and Z ４１ are each independently a hydrocarbon group having 1 to 10 carbon atoms, p is an integer from 0 to 196; and q is an integer from 0 to 10. A polymer comprising a repeating unit derived from a monomer (1) represented by the following formula:

2. X is X １ and X ２ is a divalent group consisting 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 a group consisting of one or more selected from the group consisting of -, -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); X ２ is a direct bond or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent.

3. X is -X １ -X ２ The polymer according to claim 2, wherein

4. The polymer of claim 1 , wherein n is 1.

5. Z １ are each independently a hydrocarbon group having 1 to 10 carbon atoms.

6. The polymer of claim 1 , wherein n is 2.

7. The polymer of claim 6 , wherein p is 0.

8. 2. The polymer according to claim 1, further comprising a repeating unit derived from a hydrophobic monomer (2) having a hydrocarbon group having 2 to 40 carbon atoms.

9. The polymer according to claim 8, wherein the hydrocarbon group in the hydrophobic monomer (2) is a linear alkyl group having 10 or more carbon atoms.

10. The hydrophobic monomer (2) is represented by 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 direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -S-, -C(=O)-, -S(=O) ２ - and -NR Ｃ１ - (R Ｃ１ is a divalent to tetravalent group consisting of at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms, k is 1 to 3; R ｄ is a hydrocarbon group having 2 to 40 carbon atoms. The polymer according to claim 8 , which is a monomer represented by the formula:

11. The polymer according to claim 8, wherein the content of the hydrophobic monomer (2) is 20% by weight or more based on the weight of the polymer.

12. The polymer according to claim 11, wherein the content of the monomer unit (1) is 0.5% by weight or more based on the weight of the polymer.

13. The polymer according to claim 11, 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.

14. The polymer according to claim 13, wherein the content of the monomer unit (1) is 5% by weight or more based on the weight of the polymer.

15. The polymer according to claim 1, which is a non-fluorinated polymer.

16. 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-(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), 2. The polymer according to claim 1, wherein each r is independently an integer from 1 to 22.

17. Each Y is independently an alkyl group having 1 to 3 carbon atoms; n is 2; p is 0, q is 0; Z ２ is -O-, Z ３ each independently represents an alkyl group having 1 to 3 carbon atoms or -OSiZ ３１ ３ and Z ３１ are each independently an alkyl group having 1 to 3 carbon atoms, Z ４ each independently represents an alkyl group having 1 to 3 carbon atoms or -OSiZ ４１ ３ and Z ４１ and each independently represent an alkyl group having 1 to 3 carbon atoms.

18. 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-(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), Each r is independently an integer from 1 to 22; Each Y is independently an alkyl group having 1 to 3 carbon atoms; n is 2; p is 0, q is 0; Z ２ is -O-, Z ３ each independently represents an alkyl group having 1 to 3 carbon atoms or -OSiZ ３１ ３ and Z ３１ are each independently an alkyl group having 1 to 3 carbon atoms, Z ４ each independently represents an alkyl group having 1 to 3 carbon atoms or -OSiZ ４１ ３ and Z ４１ and each independently represent an alkyl group having 1 to 3 carbon atoms.

19. A composition comprising the polymer according to any one of claims 1 to 18 and an emulsifier.

20. 20. The composition of claim 19 comprising water.

21. A water repellent comprising the polymer of claim 1 or the composition of claim 19.

22. The method for producing a water repellent according to claim 21, comprising a step of reacting the monomer (1) in a medium containing the monomer (1) and at least one selected from the group consisting of urethane, paraffin wax, silica, and silicone to obtain a polymer.

23. A water-repellent textile product comprising a textile substrate to which the polymer according to any one of claims 1 to 18 is adhered.

24. The fiber base material -SO ３ M １ (In the formula, M １ represents a monovalent cation), -COOM ２ (In the formula, M ２ represents a monovalent cation), and -O-P(O)(OX １ ) (O.X. ２ ) (wherein, X １ and X ２ each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms),

25. A method for producing a water-repellent textile product, comprising applying the water repellent agent according to claim 21 to a textile substrate.

26. Before applying the water repellent to the textile substrate, -SO ３ M １ (In the formula, M １ represents a monovalent cation), -COOM ２ (In the formula, M ２ represents a monovalent cation), and -O-P(O)(OX １ ) (O.X. ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.

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