Non-fluorinated copolymer, antifouling oil-repellent composition, and textile article

Abstract

The non-fluorinated copolymer of the present disclosure has a unit m1 based on X1‑A1‑B1 and a unit m2 based on CH2=CR1‑G‑[(C2H4O)q1(C4H8O)q2]‑R2, and the proportion of the unit m2 is 30 mass% or more of all constituent units.　X1 is a monovalent polymerizable reactive group; A1 is a divalent organic group; B1 is a monovalent organic group having at least one trialkylsilyl group; R1 is a hydrogen atom or a methyl group; G is C(=O)O‑(CH2)r (where r is an integer from 0 to 4), and the like; R2 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and the like; q1 is 3 to 100; and q2 is 0 to 50.

Description

Non-fluorinated copolymers, antifouling and oil-repellent compositions, and textile articles

[0001] This disclosure relates to non-fluorinated copolymers, antifouling and oil-repellent compositions, and textile articles.

[0002] Conventionally, various compositions have been provided as processing agents for water-repellent, oil-repellent, and stain-resistant treatments of clothing, depending on the purpose. For example, for workwear such as work clothes and linen such as rental sheets, SR processing agents containing fluorine-containing polymers that combine water-repellent and oil-repellent properties to make it difficult for dirt to adhere, and SR properties (soil-release properties) to make it easy to remove dirt once it has adhered by wiping or washing, have been commonly used.

[0003] However, fluorine-containing polymers cannot eliminate concerns about their environmental impact. Therefore, the use of non-fluorine polymers with a lower environmental impact is being considered. For example, Patent Document 1 discloses the use of a non-fluorine polymer obtained by polymerizing specific non-fluorinated ethylenically unsaturated monomers having cyclic or acyclic sugar alcohol moieties in their molecules to treat fabrics.

[0004] Japanese Patent Publication No. 2020-143291

[0005] However, articles treated with the non-fluorine polymer disclosed in Patent Document 1 have insufficient oil repellency. Therefore, it is not possible to adequately impart both dirt-removing properties and oil repellency to the articles.

[0006] This disclosure provides a non-fluorine copolymer that yields articles with excellent stain removal properties and oil repellency, an anti-fouling oil-repellent composition containing the non-fluorine copolymer, and articles with excellent stain removal properties and oil repellency.

[0007] This disclosure includes, but is not limited to, the following embodiments: [1] A non-fluorinated copolymer having units based on monomers represented by formula 1 and units based on monomers represented by formula 2, wherein the proportion of units based on monomers represented by formula 2 is 30% by mass or more of the total constituent units. １ -A １ -B １ ...Formula 1 In Formula 1, X １ A is a monovalent polymerizable reactive group, １ is a divalent organic group, B１ is a monovalent organic group having at least one trialkylsilyl group. CH ２ =CR １ -G-[(C ２ H ４ O) ｑ１ (C ４ H ８ O) ｑ２ -R ２ ... Formula 2 In Formula 2, R １ is a hydrogen atom or a methyl group, G is C(=O)O-(CH ２ ) ｒ - or -C(=O)O-(CH ２ ) ｔ -NH C(=O)O-, r is an integer from [0] to [4], t is an integer from [1] to [4], R ２ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a (meth)acryloyl group or a glycidyl group, q １ is an integer from [3] to

[100] , q ２ is an integer from [0] to

[50] . [2] The non-fluorine copolymer according to [1], wherein the trialkylsilyl group is a trimethylsilyl group. [3] The non-fluorine copolymer according to [1] or [2], further having either or both of a unit based on a monomer represented by the following formula 3 and a unit based on a monomer represented by the following formula 4. CH ２ =CR ３ -M １ -Q １ -NR ４ R ５ ... Formula 3 CH ２ =CR ６ -M ２ -Q ２ -N(O)R ７ R[[ID=C58]] ８ ... Formula 4 In Formula 3 and Formula 4, R ３ and R ６ are each independently a hydrogen atom or a methyl group, M １ and M ２ are each independently -C(=O)O- or -C(=O)NH-, Q １ and Q ２ are each independently an alkylene group having 2 to 4 carbon atoms or an alkylene group having 2 to 3 carbon atoms in which part or all of the hydrogen atoms are substituted with hydroxyl groups, R４ , R ５ , R ７ and R ８ Each of these is independently a benzyl group, a C1-C8 alkyl group, and a C2-C3 alkyl group in which some of the hydrogen atoms are replaced by hydroxyl groups, R ４ , R ５ The nitrogen atom may form a piperidino group or a pyrrolidinyl group, R ７ , R ８ The oxygen atom and nitrogen atom may form a morpholino group. [4] The nonfluorine copolymer according to any one of [1] to [3], wherein the proportion of units based on the monomer represented by formula 2 is 35% by mass or more of the total constituent units of the nonfluorine copolymer. [5] In formula 2, q １ is an integer between 3 and 50, and q ２ a non-fluorinated copolymer according to any of [1] to [4], wherein is an integer from 1 to 50. [6] Having two or more units based on the monomer represented by formula 2, wherein the two or more units are the q １ is 3 to 50 and the aforementioned q ２ A unit based on a monomer in which q is 0, and the q １ is 3 to 50 and the aforementioned q ２ A nonfluorine copolymer according to any one of [1] to [5], having at least units based on monomers in which is 1 to 50. [7] In the nonfluorine copolymer, the q １ is 3 to 50 and the aforementioned q ２ For units based on monomers where q is 0, １ is 3 to 50 and the aforementioned q ２ [6] A nonfluorinated copolymer according to [6], wherein the mass ratio of units based on monomers of which is 1 to 50 is 0.1 to 2.0. [8] A nonfluorinated copolymer according to any one of [1] to [7] having an anionic group at the end of the main chain. [9] A nonfluorinated copolymer according to [8], wherein the anionic group is a carboxyl group.

[10] The X １ is a (meth)acryloyloxy group or a hydrolyzable silyl group, and the B １ The nonfluorine copolymer according to any one of [1] to [9], wherein the silicon number is 10 or less.

[11] The B １is a monovalent organic group represented by the following formula 5 or a monovalent organic group represented by the following formula 6, and is the non-fluorine copolymer according to any one of [1] to

[10] . Ａ１ * - Si(OSiR １５ ３ ) ３－ｂ R １６ ｂ ... Formula 5 Ａ１ * - SiR １７ ２ (OSiR １８ ２ ) ｎ OSiR １９ ３ ... Formula 6 In Formula 5, b is an integer of 0 to 2, and R １５ are each independently - OSiR １５１ ３ , - R １５２ - Si(OSiR １５１ ３ ) ３－ｃ R １５３ ｃ , or a linear or branched alkyl group having 1 to 6 carbon atoms, and R １５１ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, R １５２ is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, and R １５３ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, c is an integer of 0 to 2, and R １６ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, Ａ１＊ - is a bond with A １ . In Formula 6, R １７ , R １８ and R １９ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, n is an integer of 0 or more, Ａ１＊ - is a bond with A １ .

[12] The non-fluorine copolymer according to any one of [1] to

[11] , wherein R １５ in the formula 5 is a methyl group.

[13] The non-fluorine copolymer according to any one of [1] to

[11] , wherein R １９ in the formula 6 is a methyl group.

[14] The above B １The non-fluorine copolymer according to any one of [1] to

[13] , wherein is a monovalent organic group represented by the following formula 51, a monovalent organic group represented by the following formula 52, or a monovalent organic group represented by the following formula 61.

[0008]

[0009]

[0010] In formulas 51, 52, and 61, Ａ１ * is A １ The bond is with, where n is an integer from 0 to 3 in formula 61.

[15] The nonfluorine copolymer according to any one of [1] to

[14] , wherein the proportion of units based on the monomer represented by formula 1 is 25% by mass or more of the total constituent units of the nonfluorine copolymer.

[16] The nonfluorine copolymer according to any one of [1] to

[15] , wherein the proportion of units based on the monomer represented by formula 1 is 32 to 65% by mass of the total constituent units of the nonfluorine copolymer.

[17] The nonfluorine copolymer according to any one of [1] to

[16] , wherein the proportion of units based on the monomer represented by formula 2 is 35 to 50% by mass of the total constituent units of the nonfluorine copolymer.

[18] The nonfluorine copolymer according to any one of [1] to

[17] , wherein the mass ratio of units based on the monomer represented by formula 1 to units based on the monomer represented by formula 2 in the nonfluorine polymer is 1.2 to 1.7.

[19] The non-fluorinated copolymer according to [3], wherein the proportion of units based on the monomer represented by formula 3 and units based on the monomer represented by formula 4 is 0.1 to 9% by mass of all constituent units of copolymer A.

[20] The non-fluorinated copolymer according to [3], wherein the proportion of units based on the monomer represented by formula 3 and units based on the monomer represented by formula 4 is 0.9 to 5% by mass of all constituent units of copolymer A.

[21] An antifouling and oil-repellent composition comprising the non-fluorinated copolymer according to any one of [1] to

[20] .

[22] The non-fluorinated copolymer according to any one of [1] to

[21] for use in textiles.

[23] A textile article treated with the antifouling and oil-repellent composition according to

[21] .

[0011] According to one embodiment of the present invention, a non-fluorine copolymer can be obtained that yields an article with excellent stain removal properties and oil repellency, an anti-fouling oil-repellent composition containing the non-fluorine copolymer, and an article with excellent stain removal properties and oil repellency can be provided.

[0012] The meanings and definitions of terms used in this disclosure are as follows: "Non-fluorinated polymer" is a polymer that does not contain fluorine atoms. "Fluorine atom-free" means that the fluorine atom content relative to the total mass of the polymer is 0.1% by mass or less, preferably 0% by mass. The fluorine atom content relative to the total mass of the polymer can be measured by combustion ion chromatography or the like. "Monomer-based unit" is an atomic group of a structure formed by the polymerization of one monomer molecule. The unit may be an atomic group directly formed by the polymerization of monomers, or it may be an atomic group obtained by chemically transforming a part of an atomic group formed by the polymerization of another monomer with a partially different structure. "(meth)acrylate" is a general term for acrylate and methacrylate. Similarly, "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group, and "(meth)acryloyloxy group" is a general term for acryloyloxy group and methacryloyloxy group, and the same applies to (meth)acrylic acid, (meth)acrylamide, and others. The number-average molecular weight (hereinafter also referred to as "Mn") and weight-average molecular weight (hereinafter also referred to as "Mw") of the non-fluorinated copolymer are polymethyl methacrylate-equivalent molecular weights obtained by measuring using gel permeation chromatography (hereinafter also referred to as "GPC") with a calibration curve prepared using a standard polymethyl methacrylate sample. The solid content concentration is calculated by (solid content mass / sample mass) × 100, where the mass of the sample before heating is the sample mass and the mass after drying the sample in a convection dryer at 120°C for 4 hours is the solid content mass. The "~" indicating a numerical range means that the values ​​described before and after it are included as the lower and upper limits. In numerical ranges described stepwise in this specification, the upper or lower limit described in one numerical range may be replaced with the upper or lower limit of another numerical range described stepwise. Also, in numerical ranges described in this specification, the upper or lower limit described in one numerical range may be replaced with the values ​​shown in the examples.

[0013] ≪Non-fluorinated copolymer≫ The non-fluorinated copolymer of this embodiment (hereinafter also referred to as "copolymer A") has units (hereinafter also referred to as "unit m1") based on a monomer represented by formula 1 described later (hereinafter also referred to as "monomer m1") and units (hereinafter also referred to as "unit m2") based on a monomer represented by formula 2 described later (hereinafter also referred to as "monomer m2"). In copolymer A, the proportion of unit m2 is 30% by mass or more of the total constituent units.

[0014] Copolymer A may further have either or both units based on the monomer represented by formula 3 described below (hereinafter also referred to as "monomer m3") (hereinafter also referred to as "unit m3") and units based on the monomer represented by formula 4 described below (hereinafter also referred to as "monomer m4") (hereinafter also referred to as "unit m4").

[0015] Copolymer A may further have units other than units m1, m2, m3, and m4 (hereinafter also referred to as "unit m5"). Unit m5 is a unit based on monomers other than monomers m1, m2, m3, and m4 (hereinafter also referred to as "monomer m5").

[0016] <Unit m1> Copolymer A has unit m1. Unit m1 is a unit based on monomer m1 represented by the following formula 1. X １ -A １ -B １ Formula 1 In formula 1, X １ A is a monovalent polymerizable reactive group, １ is a divalent organic group, B １ This is a monovalent organic group having at least one trialkylsilyl group.

[0017] (Polymerizable reactive group: X) １ ) X １Examples of polymerizable reactive groups include groups having polymerizable carbon-carbon double bonds and hydrolyzable silyl groups, with groups having polymerizable carbon-carbon double bonds being preferred. Examples of polymerizable carbon-carbon double bonds include vinyl groups, vinyloxy groups, allyl groups, allyloxy groups, isopropenyl groups, 1-propenyl groups, fumarate groups, maleimide groups, styryl derivative groups represented by formula 7 below, and monovalent groups represented by formula 8 below, with monovalent groups represented by formula 8 below being preferred.

[0018]

[0019] In formula 7, R １０１ ~R １０５ One of them is A １ The bond is with , and the others are, independently, a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent hydrocarbon group which may be halogenated by a halogen other than a fluorine atom.

[0020] R １０１ ~R １０５ In this, a monovalent hydrocarbon group is preferably an alkyl group having 1 to 4 carbon atoms. １０１ ~R １０５ Of these, A １ Those that are not bonded to the other are preferably monovalent hydrocarbon groups that may be halogenated with a hydrogen atom or a halogen other than fluorine, and more preferably hydrogen atoms.

[0021] * Ａ１ -R １１ C(=O)CR １３ =CH ２ ...Formula 8 In Formula 8, R １１ is a single bond, oxygen atom, or NR １２ It is a divalent group represented by R １３ * is a hydrogen atom, a halogen atom other than a fluorine atom, or a linear or branched alkyl group having 1 to 12 carbon atoms. Ａ１ is A １ This is a combination of R. １２ This is a hydrogen atom or a monovalent organic group.

[0022] R １１ is an oxygen atom, or NR １２A divalent group represented by R is preferred. １２ The monovalent organic groups in this include linear or branched alkyl groups having 1 to 12 carbon atoms, and -A １ -B １ Examples include: A １ and B １ These are A in Equation 1, respectively. １ and B １ It is similar to that.

[0023] R １２ The hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms is preferred, a hydrogen atom or a methyl group is more preferred, and a hydrogen atom is even more preferred. １３ The hydrogen atom, chlorine atom, and a linear alkyl group having 1 to 12 carbon atoms are preferred, a hydrogen atom and a methyl group are more preferred, and a methyl group is even more preferred. １１ is an oxygen atom, R １３ When is a hydrogen atom or a methyl group, formula 8 represents a (meth)acryloyloxy group. １１ NR １２ A divalent group represented by R １３ When is a hydrogen atom or a methyl group, formula 8 represents a (meth)acrylamide group. The monovalent group represented by formula 8 is preferably a (meth)acryloyloxy group or a (meth)acrylamide group.

[0024] Examples of hydrolyzable silyl groups include the monovalent group represented by formula 9 below.

[0025] * Ａ１ -SiR １４ ３－ａ X ａ ...Formula 9 In formula 9, R １４ X is a monovalent organic group having 1 to 20 carbon atoms, excluding hydrolyzable groups. X represents a hydroxyl group, a halogen atom excluding fluorine, or a hydrolyzable group. a is an integer of 2 or 3. Multiple X values ​​may be the same or different. * Ａ１ - is A １ This is a combination of the two.

[0026] R １４The group is preferably at least one group selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, α-chloroalkyl groups, and triorganosiloxy groups. １４ Specifically, preferred groups include linear or branched alkyl groups having 1 to 4 carbon atoms, cyclohexyl groups, phenyl groups, benzyl groups, α-chloromethyl groups, trimethylsiloxy groups, triethylsiloxy groups, and triphenylsiloxy groups.

[0027] Examples of hydrolyzable groups of X include alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, sulfanyl groups, and alkenyloxy groups. As the hydrolyzable group of X, alkoxy groups are preferred because they exhibit mild hydrolysis and are easy to handle. Methoxy groups, ethoxy groups, and isopropoxy groups are preferred, with methoxy and ethoxy groups being more preferred. When the alkoxy group is a methoxy or ethoxy group, siloxane bonds are readily formed.

[0028] Examples of hydrolyzable silyl groups represented by formula 9 include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, methyldiisopropoxysilyl group, (α-chloromethyl)dimethoxysilyl group, and (α-chloromethyl)diethoxysilyl group. Among these, trimethoxysilyl group, triethoxysilyl group, dimethoxymethylsilyl group, and diethoxymethylsilyl group are preferred, and dimethoxymethylsilyl group is more preferred.

[0029] (Divalent organic group: A) １ ) A １As the divalent organic group, a divalent hydrocarbon group is preferred. Examples of divalent hydrocarbon groups include linear or branched alkylene groups, cycloalkylene groups, groups in which at least one of the carbon-carbon single bonds of the alkylene group is replaced with a carbon-carbon double bond or a carbon-carbon triple bond (e.g., alkenylene group, alkylylene group), groups in which at least one of the carbon-carbon single bonds of the cycloalkylene group is replaced with a carbon-carbon double bond, and arylene groups. Among these, linear or branched alkylene groups and cycloalkylene groups are preferred, linear or branched alkylene groups are more preferred, and linear alkylene groups are even more preferred. The carbon in the divalent hydrocarbon group may be replaced with a heteroatom or a divalent group having a heteroatom. The hydrogen in the hydrocarbon group may be replaced with a halogen atom or a monovalent group having a heteroatom. Examples of heteroatoms include nitrogen, oxygen, sulfur, boron, and phosphorus atoms, with nitrogen and oxygen atoms being preferred. Examples of divalent groups having heteroatoms include amide groups, urethane groups, urea groups, carbonyl groups, and ester groups. Examples of monovalent groups having heteroatoms include hydroxyl groups, mercapto groups, amino groups, and monovalent groups including the divalent groups having heteroatoms mentioned above. A １ It does not contain silicon atoms.

[0030] A １ The number of carbon atoms is preferably 2 to 20, more preferably 2 to 16, even more preferably 2 to 10, and particularly preferably 2 to 6.

[0031] A １ Preferably, the alkylene group is a linear alkylene group having 1 to 8 carbon atoms, such as a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, and octylene group; more preferably, a branched alkylene group in which at least one hydrogen atom of the linear alkylene group is substituted with an alkyl group having 1 to 3 carbon atoms, such as a methyl group, ethyl group, and propyl group; and more preferably, the linear alkylene group. １ Specific examples include: Ｘ１＊ - [CH ２ C(O)NH] ｎ１ (CH ２ ) ３ -＊Ｂ１ , and Ｘ１＊ - [CH ２ C(O)NH] ｎ１ CH ２ CH (CH ３ ) - ＊Ｂ１ These include, Ｘ１＊ - (CH ２ ) ３ - ＊Ｂ１ A is preferable. １ In the specific example, n1 is an integer between 0 and 3, and preferably an integer between 0 and 2. Ｘ１＊ - is X １ This is a combination of - ＊Ｂ１ is B １ This is a combination of the two.

[0032] (A monovalent organic group having at least one trialkylsilyl group: B) １ ) B １ The number of trialkylsilyl groups in the compound is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 3. Furthermore, one embodiment of the present disclosure is B １ The number of trialkylsilyl groups in the copolymer is preferably 2 to 9, more preferably 2 to 6, and even more preferably 2 to 3. When the number of trialkylsilyl groups is within the above numerical range, the oil repellency of the article treated with copolymer A is better. B １ If the compound has two or more trialkylsilyl groups, the multiple trialkylsilyl groups may be the same or different.

[0033] The alkyl group of the trialkylsilyl group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a t-butyl group, isopropyl group, ethyl group, and methyl group, even more preferably an ethyl group and a methyl group, and particularly preferably a methyl group. The three alkyl groups of the trialkylsilyl group may be the same or different. The trimethylsilyl group is preferred as the trialkylsilyl group.

[0034] B １ It is preferable that it has a siloxane bond. １The number of Si-O bonds in the copolymer is preferably 1 to 80, more preferably 1 to 20, even more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 2 to 5. When the number of Si-O bonds is within the above range, the oil repellency of the article treated with copolymer A is better. B １ The silicon number is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 8, even more preferably 1 to 6, particularly preferably 2 to 5, and most preferably 3 to 4.

[0035] A １ B combines with １ The atom inside is preferably a silicon atom. B １ Preferably, the monovalent organic group represented by formula 5 below or the monovalent organic group represented by formula 6 below is preferred, and the monovalent organic group represented by formula 5 below is more preferred. In formulas 5 and 6 below, Ａ１ *- is A １ This is a combination of the two.

[0036] Ａ１ *-Si(OSiR １５ ３ ) ３－ｂ R １６ ｂ ...Equation 5 Ａ１ *-SiR １７ ２ (OSiR １８ ２ ) ｎ OSiR １９ ３ ...Formula 6

[0037] In equation 5, b is an integer between 0 and 2. １５ These are each independently of -OSiR １５１ ３ , -R １５２ -Si(OSiR) １５１ ３ ) ３－ｃ R １５３ ｃ or a linear or branched alkyl group having 1 to 6 carbon atoms. １５１ Each of these is independently a linear or branched alkyl group having 1 to 6 carbon atoms, and R １５２ R is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, １５３ ​Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms, where c is an integer from 0 to 2. １６ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms. Ａ１＊ - is A １ This is a combination of the two.

[0038] b is preferably 0 or 1, and particularly preferably 0. １５ , R １５１ , R １５３ and R １６ The linear or branched alkyl group in formula 5 is preferably a t-butyl group, an isopropyl group, an ethyl group, and a methyl group, more preferably an ethyl group and a methyl group, and even more preferably a methyl group. １５ and R １６ If there are multiple, R １５ and R １６ These may be the same or different. １５２ In formula 5, the linear or branched alkylene group is preferably a methylene group or an ethylene group, and more preferably an ethylene group. c is preferably 0. In formula 5, multiple R １５ These may be the same or different. １５ ga-OSiR １５１ ３ If so, multiple R １５１ These may be the same or different. If b is 2, there are multiple R １６ These can be the same or different. If c is 2, there are multiple R １５３ These may be the same or different. In one preferred embodiment, R １５ and R １６ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms.

[0039] In formula 6, R １７ , R １８ and R １９ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms. n is an integer greater than or equal to 0. Ａ１＊ - is A １ This is a combination of the two.

[0040] From the viewpoint of oil repellency, n is preferably an integer between 0 and 10, more preferably an integer between 0 and 6, and even more preferably an integer between 0 and 3. １７ , R １８ and R １９ The linear or branched alkyl groups in are preferably t-butyl, isopropyl, ethyl, and methyl groups, more preferably ethyl and methyl groups, and even more preferably methyl groups. １７ , R １８ and R １９ These may be the same or different.

[0041] As the monovalent organic group represented by formula 5 above, a monovalent organic group represented by formula 51 or formula 52 below is preferred. In formula 51 or 52, Ａ１ *- is A １ This is a combination of the two.

[0042]

[0043] As the monovalent organic group represented by the above formula 6, the monovalent organic group represented by the following formula 61 is preferred. In formula 61, Ａ１ *- is A １ This is a combination of the two.

[0044]

[0045] In equation 61, n is the same as n in equation 6.

[0046] The molecular weight of monomer m1 is preferably less than 1,000, more preferably less than 500, and even more preferably 450 or less, from the viewpoint of oil repellency. It is also preferably 200 or more, and more preferably 300 or more. The molecular weight of monomer m1 is preferably 200 or more and less than 1,000, more preferably 200 or more and less than 500, and even more preferably 300 to 450, from the viewpoint of oil repellency. In particular, B in monomer m1 １ When is a group represented by formula 5, the molecular weight of monomer m1 is preferably 200 or more and less than 1,000, more preferably 200 or more and less than 500, and even more preferably 300 to 450. B in monomer m1 １ When is a group represented by formula 6, the molecular weight of monomer m1 is preferably 200 or more and less than 1,000.

[0047] Examples of monomer m1 include 3-(1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxanyl)propyl (meth)acrylate, 3-((meth)acryloyloxy)propyltris(trimethylsiloxy)silane, 3-((meth)acryloyloxy)propylbis(trimethylsiloxy)methylsilane, and N-(tris(trimethylsiloxy)silylpropyl)(meth)acrylamide, with 3-((meth)acryloyloxy)propyltris(trimethylsiloxy)silane, 3-((meth)acryloyloxy)propylbis(trimethylsiloxy)methylsilane, and N-(tris(trimethylsiloxy)silylpropyl)(meth)acrylamide being more preferred.

[0048] Monomer m1 may be used alone or in combination of two or more types.

[0049] <Unit m²> Copolymer A has a unit m². The unit m² is a unit based on monomer m² represented by the following formula 2. Monomer m² may be used alone or in combination of two or more types, and it is preferable to use two or more types in combination. CH ２ =CR １ -G-[(C ２ H ４ O) ｑ１ (C ４ H ８ O) ｑ２ ]-R ２ ...Formula 2

[0050] In formula 2, R １ G is a hydrogen atom or a methyl group, with a methyl group being preferred. G is C(=O)O-(CH ２ ) ｒ - or -C(=O)O-(CH ２ ) ｔ -NHC(=O)O- and C(=O)O-(CH ２ ) ｒ - is preferred. r is an integer from 0 to 4, preferably 0 to 3, more preferably 0 to 2, even more preferably 0 or 1, and most preferably 0. t is an integer from 1 to 4. q １q is an integer between 3 and 100, preferably between 3 and 50, more preferably between 4 and 40, even more preferably between 4 and 30, even more preferably between 4 and 20, particularly preferably between 4 and 9, and most preferably between 5 and 9. ２ x is an integer from 0 to 50, preferably 1 to 50, more preferably 1 to 40, even more preferably 1 to 30, particularly preferably 1 to 20, and most preferably 1 to 10.

[0051] When using two or more monomers m2 in combination, the unit m2 is defined as q in formula 2, from the viewpoint of oil repellency and dirt removal properties. ２ A unit based on a monomer where q is 0 (hereinafter also referred to as "monomer m2-1"), and in equation 2, q ２ It is preferable to have a unit (hereinafter also referred to as "unit m2-2") based on a monomer (hereinafter also referred to as "monomer m2-2") in which q is 1 or more. As for unit m2, from the viewpoint of oil repellency and dirt removal, q １ is 3 to 50 and q ２ The units and q based on monomer m²-1 where is 0 １ is 3 to 50 and q ２ It is preferable that the unit has monomer m2-2 in which is 1 to 50, １ is 4 to 20 and q ２ The units and q based on monomer m²-1 where is 0 １ is 4 to 20 and q ２ It is more preferable that the unit has monomer m2-2 in which is 1 to 20, １ is 4 to 9 and q ２ The units and q based on monomer m²-1 where is 0 １ is 4 to 20 and q ２ It is even more preferable that the unit has monomer m2-2, where is 1 to 10.

[0052] In formula 2, R ２ The group is a hydrogen atom, a C1-C8 alkyl group, a (meth)acryloyl group, or a glycidyl group, with a hydrogen atom and a C1-C8 alkyl group being preferred, a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group being more preferred, a hydrogen atom and a methyl group being even more preferred, and a methyl group being particularly preferred. In particular, q ２ If R is 0,２ It is preferable that it be a methyl group.

[0053] q in Equation 2 ２ If it is 1 or greater, -C ２ H ４ O- and -C ４ H ８ The O- copolymer chain may be a random copolymer chain or a blocked copolymer chain. (C) ２ H ４ O) is written as "EO", (C ４ H ８ O) is sometimes written as "TO".

[0054] A suitable monomer m2 is polyethylene oxide monoacrylate (CH ２ =CHCOO(EO) ｑ１ H), polyethylene oxide monomethacrylate (CH ２ = C(CH ３ ) COO (EO) ｑ１ H), Methoxypolyethylene oxide monoacrylate (CH ２ =CHCOO(EO) ｑ１ CH ３ ), methoxypolyethylene oxide monomethacrylate (CH ２ = C(CH ３ ) COO (EO) ｑ１ CH ３ ), poly(ethylene oxide-tetramethylene oxide) monoacrylate (CH ２ =CHCOO-[(EO) ｑ１ - (TO) ｑ２ ]-H), poly(ethylene oxide-tetramethylene oxide) monomethacrylate (CH ２ = C(CH ３ )COO-[(EO) ｑ１ - (TO) ｑ２ ]-H), Methoxypoly(ethylene oxide-tetramethylene oxide) monoacrylate (CH ２ =CHCOO-[(EO) ｑ１ - (TO) ｑ２ ]-CH ３ ), methoxypoly(ethylene oxide-tetramethylene oxide) monomethacrylate (CH ２= C(CH ３ )COO-[(EO) ｑ１ - (TO) ｑ２ ]-CH ３ ), polyethylene oxide diacrylate (CH ２ =CHCOO(EO) ｑ１ CO = CH ２ ), polyethylene oxide dimethacrylate (CH ２ = C(CH ３ ) COO (EO) ｑ１ CO = CH ２ ), poly(ethylene oxide-tetramethylene oxide) diacrylate (CH ２ =CHCOO-[(EO) ｑ１ - (TO) ｑ２ ]-CO=CH ２ ), poly(ethylene oxide-tetramethylene oxide) dimethacrylate (CH ２ = C(CH ３ )COO-[(EO) ｑ１ - (TO) ｑ２ ]-CO=CH ２ Examples are given, but monomer m2 is not limited to these examples.

[0055] Monomer m2 may be synthesized or a commercially available product may be used. Examples of commercially available monomer m2 include "NK Ester M-90G", "NK Ester M-130G", "NK Ester M-230G", "NK Ester M-450G", "NK Ester AM-90G", "NK Ester AM-130G", and "NK Ester AM-230G" from Shin Nakamura Chemical Industry Co., Ltd., and "Bremmer PE-200", "Bremmer PE-350", "Bremmer PE-350G", "Bremmer AE-200", "Bremmer AE-400", "Bremmer PME-200", "Bremmer PME-400", "Bremmer PME-550", "Bremmer PME-1000", "Bremmer PME-4000", "Bremmer AME-400", and "Bremmer 55PET-800" from NOF Corporation.

[0056] <Units m3, Units m4> Copolymer A may further have either or both of units m3 and m4. Unit m3 is a unit based on monomer m3 represented by the following formula 3, and unit m4 is a unit based on monomer m4 represented by the following formula 4. CH ２ =CR ３ -M １ - Q １ -NR ４ R ５ ...Formula 3 CH ２ =CR ６ -M ２ - Q ２ -N(O)R ７ R ８ ...Formula 4

[0057] In equations 3 and 4, R ３ and R ６ Each is independently a hydrogen atom or a methyl group, M １ and M ２ Each of these is independently -C(=O)O- or -C(=O)NH-, and Q １ and Q ２ Each of these is independently an alkylene group having 2 to 4 carbon atoms or an alkylene group having 2 to 3 carbon atoms in which some or all of the hydrogen atoms are replaced by hydroxyl groups, R ４ , R ５ , R ７ and R ８ Each of these is independently a benzyl group, a C1-C8 alkyl group, and a C2-C3 alkyl group in which some of the hydrogen atoms are replaced by hydroxyl groups, R ４ , R ５ The nitrogen atom may form a piperidino group or a pyrrolidinyl group, R ７ , R ８ The oxygen and nitrogen atoms may form morpholino groups.

[0058] In equations 3 and 4, M １ and M ２ Each of these is independently preferable to be -C(=O)O-. Q １ and Q ２ Each of these is preferably an alkylene group having 2 to 4 carbon atoms. ４ , R ５ , R ７ and R ８Each of these is preferably an alkyl group having 1 to 4 carbon atoms.

[0059] Examples of suitable monomers m3 and m4 include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-diisopropylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N-(meth)acryloylmorpholine, N-(meth)acryloylpepyridine, N,N-dimethylaminooxideethyl (meth)acrylate, and N,N-diethylaminooxideethyl (meth)acrylate, but monomers m3 and m4 are not limited to these examples.

[0060] <Anionic Groups> Copolymer A preferably has anionic groups at the ends of its main chain. The amount of anionic groups in copolymer A that is sufficient to obtain the effect of the anionic groups is preferably 0.1% by mass or more, and more preferably 0.3% by mass or more, of the total mass of copolymer A. The upper limit of the amount of anionic groups is determined by considering the ionic balance in copolymer A and is not particularly limited. The upper limit may be, for example, 3.0% by mass or less, 2.0% by mass or less, etc. Having anionic groups at the ends of the main chain provides better dirt removal than having anionic groups at the ends of the side chains.

[0061] An anionic group is a group that can ionize in water to form an anion. For example, one or more groups selected from the group consisting of carboxyl groups, sulfonic acid groups, phosphoric acid groups, chloric acid groups, nitrate groups, and manganic acid groups are preferred. Among these, carboxyl groups are preferred. These acid groups may form salts or esters. Two or more anionic groups may be present in one molecule of copolymer A.

[0062] The method for introducing anionic groups to the main chain ends of copolymer A is not particularly limited. A simple method is to use either or both an initiator having an anionic group and a chain transfer agent having an anionic group during copolymerization. The anionic groups of the initiator and the chain transfer agent are preferably carboxyl groups, which are weakly acidic in terms of acidity. The carboxyl groups of the initiator and the chain transfer agent may form salts or esters.

[0063] In particular, if copolymer A has either one or both of units m3 and m4, it is preferable that it has an anionic group at the end of the main chain. When copolymer A has either one or both of units m3 and m4 having amino groups, the dispersibility of copolymer A in aqueous media and the uniform adhesion to fibrous substrates are improved. On the other hand, since amino groups are cationic, they readily adsorb dirt components. In this relationship, amino groups tend to reduce stain resistance. Therefore, by introducing anionic groups at the end of the main chain of copolymer A, the adsorption of dirt components by amino groups can be suppressed. As a result, stain resistance is expected to improve. In addition, in a stain-resistant oil-repellent composition containing copolymer A, if a crosslinking agent having strong reactivity with anionic properties is used in combination, it is also advantageous that the crosslinking site becomes the end of the main chain. If the end of the main chain becomes the crosslinking site, the fluidity of the polymer is less likely to be inhibited, and the molecular mobility necessary for stain resistance is easily maintained. As a result, good stain resistance and wash durability can be achieved at the same time.

[0064] <Unit m5> Copolymer A may further have other units m5 besides units m1, m2, m3, and m4. Unit m5 is a unit based on monomer m5 other than monomers m1, m2, m3, and m4. It is preferable that monomer m5 has a polymerizable reactive group. Examples of polymerizable reactive groups include groups having polymerizable carbon-carbon double bonds and hydrolyzable silyl groups, with groups having polymerizable carbon-carbon double bonds being preferred. Examples of groups having polymerizable carbon-carbon double bonds and hydrolyzable silyl groups include X １ Examples of groups similar to those described above are shown, and preferred embodiments are also shown in X １ It is the same as this.

[0065] X１ If the group has a polymerizable carbon-carbon double bond, it is preferable that the polymerizable reactive group of monomer m5 also has a polymerizable carbon-carbon double bond. １ The polymerizable carbon-carbon double bond groups of monomer m5 may be the same or different, but it is preferable that they be the same.

[0066] X １ If the group is a hydrolyzable silyl group, the polymerizable reactive group of monomer m5 is also preferably a hydrolyzable silyl group. １ The hydrolyzable silyl groups in monomer m5 may be the same or different, but they are preferably the same.

[0067] Monomer m5 may have a crosslinkable functional group. Examples of crosslinkable functional groups include isocyanate groups, blocked isocyanate groups, alkoxysilyl groups, primary amino groups, alkoxymethylamide groups, silanol groups, primary amide groups, epoxy groups, hydroxyl groups, oxazoline groups, carboxyl groups, and sulfonic acid groups.

[0068] Examples of monomers m5 having a polymerizable carbon-carbon double bond as a polymerizable reactive group include, but are not limited to, vinyl carboxylates, allyl carboxylates, vinyl ethers, allyl ethers, olefins, (meth)acrylates, (meth)acrylic acid, (meth)acrylamide, halogenated olefins excluding fluorine atoms, and styrene compounds.

[0069] Examples of vinyl carboxylate esters include vinyl acetate, vinyl pivalate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl octoate, vinyl monochloroacetate, divinyl adipate, vinyl methacrylate, vinyl crotonate, and vinyl cinnamate. Examples of allyl carboxylate esters include allyl acetate and diallyl adipate.

[0070] Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, chloromethyl vinyl ether, 2-chloroethyl vinyl ether, chloropropyl vinyl ether, cyclohexyl vinyl ether, ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether. Examples of allyl ethers include allyl ethyl ether, diallyl ether, 1,3-diallyloxy-2-propanol, alyloxypolyethylene glycol mono(meth)acrylate, and alyloxypoly(ethylene glycol-propylene glycol) mono(meth)acrylate. Examples of olefins include ethylene and propylene.

[0071] Examples of (meth)acrylates include alkyl (meth)acrylates that may have an amide bond, (meth)acrylates that further have crosslinkable functional groups such as hydroxyalkyl (meth)acrylates, aromatic (meth)acrylates, and aliphatic cyclic (meth)acrylates. Examples of alkyl (meth)acrylates that may have an amide bond include methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, palmitamide ethyl (meth)acrylate, palmitamide propyl (meth)acrylate, stearate ethyl (meth)acrylate, stearate propyl (meth)acrylate, behenamide ethyl (meth)acrylate, and behenamide propyl (meth)acrylate. Examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyoxyethylene glycol mono (meth)acrylate, polyoxypropylene glycol mono (meth)acrylate, and 2-hydroxy-3-acryloyloxypropyl (meth)acrylate. Examples of aromatic (meth)acrylates include phenyl (meth)acrylate and benzyl (meth)acrylate. Examples of aliphatic cyclic (meth)acrylates include cyclohexyl (meth)acrylate and isobornyl (meth)acrylate.

[0072] Examples of (meth)acrylamides include alkyl(meth)acrylamides and hydroxyalkyl(meth)acrylamides. Examples of alkyl(meth)acrylamides include N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropylacrylamide, N,N-diisopropyl(meth)acrylamide, N-(n-butyl)(meth)acrylamide, N-(t-butyl)(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, N-lauryl(meth)acrylamide, N-stearyl(meth)acrylamide, and N-behenyl(meth)acrylamide. Examples of hydroxyalkyl(meth)acrylamides include N-hydroxymethyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, and N-(4-hydroxybutyl)(meth)acrylamide.

[0073] Examples of halogenated olefins without a fluorine atom include vinyl chloride and vinylidene chloride.

[0074] Examples of styrene-based compounds include styrene, 4-chlorostyrene, 4-methylstyrene, and 4-methoxystyrene.

[0075] Examples of monomer m5 having a hydrolyzable silyl group as a polymerizable reactive group include compounds in which the polymerizable reactive group of monomer m5 having a polymerizable carbon-carbon double bond as described above is substituted with a hydrolyzable silyl group.

[0076] <Properties of Copolymer A> In one embodiment, the proportion of unit m1 is preferably 15 to 70% by mass of the total constituent units of copolymer A, more preferably 20 to 69% by mass, even more preferably 25 to 68% by mass, particularly preferably 30 to 67% by mass, and most preferably 35 to 66% by mass. When the proportion of unit m1 is above the lower limit of the above numerical range, the water repellency and oil repellency are better. When the proportion of unit m1 is below the upper limit of the above numerical range, the initial water repellency and oil repellency are better.

[0077] Furthermore, in one embodiment, the proportion of unit m1 is preferably 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more of the total constituent units of polymer A. Also, 70% by mass or less, 65% by mass or less, or 60% by mass or less are preferred. The above upper and lower limits can be combined as appropriate, and 15 to 70% by mass, 15 to 65% by mass, 25 to 65% by mass, 35 to 65% by mass, 35 to 60% by mass, or 35 to 55% by mass are preferred. When the proportion of unit m1 is within the above range, the water-repellent and oil-repellent properties are superior.

[0078] In one embodiment, the proportion of unit m2 is 30% by mass or more of the total constituent units of copolymer A. Preferably, the proportion of unit m2 is 30 to 85% by mass, more preferably 31 to 75% by mass, even more preferably 32 to 65% by mass, and particularly preferably 33 to 50% by mass. Since the proportion of unit m2 is above the lower limit of the above numerical range, excellent stain removal properties are exhibited. Since the proportion of unit m2 is below the upper limit of the above numerical range, the proportion of unit m1 can be sufficiently secured. As a result, excellent water repellency and oil repellency are exhibited.

[0079] Furthermore, in one embodiment, the proportion of unit m2 is preferably 35% by mass or more and 40% by mass or more of the total constituent units of polymer A. Also, 85% by mass or less, 75% by mass or less, 65% by mass or less, and 50% by mass or less are preferred. The above upper and lower limits can be combined as appropriate, and 30 to 85% by mass, 35 to 85% by mass, 35 to 75% by mass, 35 to 65% by mass, 35 to 50% by mass, and 40 to 50% by mass are preferred. When the proportion of unit m1 is within the above range, the water repellency and oil repellency are superior.

[0080] In polymer A, the mass ratio of unit m1 to unit m2 (unit m1 / unit m2) is preferably 0.1 to 2.0, more preferably 0.5 to 1.9, even more preferably 1.0 to 1.8, and particularly preferably 1.2 to 1.7. When the above ratio is within the above range, a good balance of oil repellency and stain removal properties is easily achieved.

[0081] When polymer A has units m2-1 and m2-2 as units m2, the mass ratio of unit m2-1 to unit m2-2 (unit m2-1 / unit m2-2) is preferably 0.01 to 2.0, more preferably 0.05 to 1.0, even more preferably 0.1 to 0.8, and particularly preferably 0.4 to 0.6. When the above ratio is within the above range, oil repellency and stain removal properties tend to be well balanced.

[0082] When copolymer A has either or both units m3 and m4, the proportion of either or both units m3 and m4 is preferably 0.1 to 9% by mass, more preferably 0.3 to 8% by mass, even more preferably 0.5 to 7% by mass, particularly preferably 0.7 to 6% by mass, and most preferably 0.9 to 5% by mass of the total constituent units of copolymer A. When the proportion of either or both units m3 and m4 is above the lower limit of the above numerical range, the dispersibility of copolymer A in aqueous media and its adhesion to textile products are improved. When the proportion of either or both units m3 and m4 is below the upper limit of the above numerical range, water repellency, oil repellency, and stain removal properties tend to be well-balanced.

[0083] When copolymer A has unit m5, the proportion of unit m5 is preferably 0.1 to 9% by mass of the total constituent units of copolymer A, more preferably 0.2 to 8% by mass, even more preferably 0.3 to 7% by mass, particularly preferably 0.4 to 6% by mass, and most preferably 0.5 to 5% by mass. If the proportion of unit m5 is above the lower limit of the above numerical range, it is easier to impart properties due to unit m5. If the proportion of unit m5 is below the upper limit of the above numerical range, it is easier to achieve a good balance of water repellency, oil repellency, and stain removal properties.

[0084] The content of each unit is １ The reaction rates of monomers m1 to m5 can be calculated by H-NMR, gas chromatography, and high-performance liquid chromatography. When copolymer A is produced, if the conversion rate of monomers m1 to m5 to copolymer A is high (for example, 90% or more), the content of each unit may be calculated based on the amount of monomers m1 to m5 charged.

[0085] The manganese (Mn) of copolymer A is preferably 1,000 to 1,000,000, more preferably 10,000 to 1,000,000, and even more preferably 10,000 to 800,000. When the Mn of copolymer A is above the lower limit of the above numerical range, the oil repellency of the article treated with copolymer A is better. When the Mn of copolymer A is below the upper limit of the above numerical range, the dispersibility in various solvents is better.

[0086] The Mw of copolymer A is preferably 1,000 to 1,000,000, more preferably 10,000 to 1,000,000, and even more preferably 10,000 to 800,000. When the Mw of copolymer A is above the lower limit of the above numerical range, the oil repellency of the article treated with copolymer A is better. When the Mw of copolymer A is below the upper limit of the above numerical range, the dispersibility in various solvents is better.

[0087] Copolymer A may be a random copolymer or a block copolymer, and is not particularly limited.

[0088] <Method for producing copolymer A> Copolymer A can be synthesized by polymerizing monomer components, which include monomers m1 and m2, and optionally at least one selected from the group consisting of monomers m3, m4, and m5. The amount of monomers to be added can be appropriately set according to the desired composition of copolymer A.

[0089] Copolymer A having anionic groups at the ends of the main chain may be synthesized by polymerizing monomer components in the presence of either or both an initiator having an anionic group and a chain transfer agent having an anionic group.

[0090] (Initiator) It is preferable to use an initiator when polymerizing copolymer A. There are no particular restrictions on the initiator, and it can be appropriately selected depending on the type of polymerizable reactive group of the monomer components. The amount of initiator added is preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total monomers.

[0091] Examples of initiators include those used in radical polymerization, cationic polymerization, and anionic polymerization. Examples of initiators used in radical polymerization include organic peroxides, inorganic peroxides, and azo compounds. Examples of initiators used in cationic polymerization include organic acids, inorganic acids, Lewis acids, thermal cationic polymerization initiators that generate these in the polymerization system, and photocatalytic cationic polymerization initiators. Examples of initiators used in anionic polymerization include organometallic compounds and photoanionic polymerization initiators that generate organic bases in the polymerization system. Initiators may be used individually or in combination of two or more types.

[0092] There are no particular restrictions on organic peroxides, but examples include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, t-butyl hydroperoxide, and t-butyl-α-cumyl peroxide. These may be used individually or in combination of two or more. There are no particular restrictions on inorganic peroxides, but examples include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, and percarbonates. These may be used individually or in combination of two or more. There are no particular restrictions on the azo compound, and examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitride), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobisisobutyrate dimethyl, and 2,2'-azobis(2-amidinopropane) dihydrochloride. These may be used individually or in combination of two or more. In addition, commercially available V-59 and V-65 (trade names, products of Fujifilm Wako Pure Chemical Industries) may be used as azo polymerization initiators. There are no particular restrictions on the organic acid, and methanesulfonic acid is an example. There are no particular restrictions on the inorganic acid, and hydrochloric acid, nitric acid, and sulfuric acid are examples. There are no particular restrictions on Lewis acids, but examples include trichloroaluminum, ethylaluminum dichloride, and ethylaluminum sesquichloride. There are no particular restrictions on thermal cationic polymerization initiators, but examples include benzyl(4-hydroxyphenyl)methylsulfonium hexafluoroantimonate. There are no particular restrictions on photocationic polymerization initiators, but examples include WPI-113, WPI-116, and WPI-170 (trade names, products of Fujifilm Wako Pure Chemical Industries). There are no particular restrictions on organometallic compounds, but examples include n-butyllithium, sec-butyllithium, t-butyllithium, diethylzinc, and triethylaluminum. There are no particular restrictions on photoanionic polymerization initiators, but examples include WPBG-266, WPBG-300, and WPBG-345 (trade names, products of Fujifilm Wako Pure Chemical Industries).

[0093] A polymerization initiator having an anionic group may be used, or a polymerization initiator without an anionic group may be used, or both may be used in combination. One initiator may be used alone, or two or more initiators may be used in combination.

[0094] Examples of initiators having an anionic group include azo compounds having a carboxyl group such as 4,4'-azobis(4-cyanovaleric acid), disuccinate peroxide, and persulfates, but are not limited to these examples. Azo compounds having a carboxyl group are more preferred, and 4,4'-azobis(4-cyanovaleric acid) is even more preferred.

[0095] Examples of polymerization initiators that do not have anionic groups include peroxides such as benzyl peroxide, lauryl peroxide, succinyl peroxide, and tert-butyl perpivalate; and azo compounds that do not have anionic groups. Examples of azo compounds that do not have anionic groups include, but are not limited to, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis[2-(2-imidazolin-2yl)propane], 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(2cyclohexane-1-carbonitride), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(1-acetoxy-1-phenylethane), and dimethylazobisisobutyrate.

[0096] The polymerization temperature is preferably 20 to 150°C, and more preferably 40 to 90°C. The polymerization time varies depending on the reaction temperature, but is for example 1 to 144 hours, preferably 3 to 86 hours. Polymerization is preferably carried out in an inert atmosphere such as nitrogen.

[0097] Examples of polymerization methods include solution polymerization, emulsion polymerization, and bulk polymerization. Solution polymerization and emulsion polymerization are preferred.

[0098] Organic solvents are preferred as the medium used in solution polymerization. There are no particular restrictions on organic solvents, but examples include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, and ester organic solvents. These may be used individually or in combination of two or more.

[0099] There are no particular restrictions on the hydrocarbon organic solvents, but examples include pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene. These may be used individually or in combination of two or more.

[0100] There are no particular restrictions on the alcohol-based organic solvents, but examples include ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol. These may be used individually or in combination of two or more.

[0101] There are no particular restrictions on the ketone-based organic solvents, but examples include methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone, and cyclohexanone. These may be used individually or in combination of two or more.

[0102] There are no particular restrictions on the ether-based organic solvents, but examples include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dibutyl ether, and diethylene glycol methyl ethyl ether. These may be used individually or in combination of two or more.

[0103] There are no particular restrictions on the ester-based organic solvents, and examples include methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxypropionate, cyclohexanol acetate, γ-butyrolactone, 3-methyl-3-methoxybutyl acetate, and glycerin triacetate. These may be used individually or in combination of two or more.

[0104] In emulsion polymerization, for example, monomer components are polymerized in an emulsion containing monomer components, an aqueous medium, an emulsifier, and a polymerization initiator. Examples of the aqueous medium include water, or a mixture of water and a water-soluble organic solvent. The water-soluble organic solvent is an organic solvent that is miscible with water in any proportion. Preferably, the water-soluble organic solvent is at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols, and aprotic polar solvents. When the aqueous medium contains a water-soluble organic solvent, the content of the water-soluble organic solvent is preferably 1 to 80 parts by mass, and more preferably 10 to 60 parts by mass, per 100 parts by mass of water.

[0105] Emulsifiers are surfactants that have both hydrophilic and hydrophobic parts. Examples of emulsifiers include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, and amphoteric emulsifiers. Non-fluorinated emulsifiers that do not contain fluorine atoms are preferred. As for emulsifiers, those similar to those described later can be used. As for emulsifiers, from the standpoint of excellent dispersion stability of the anti-fouling oil-repellent composition, the use of a nonionic emulsifier alone, a combination of a nonionic emulsifier and a cationic or amphoteric emulsifier, or the use of an anionic emulsifier alone is preferred, and the combination of a nonionic emulsifier and a cationic emulsifier is more preferred.

[0106] (Polymerization 1) When the polymerizable reactive group of monomer m1 is a group having a polymerizable carbon-carbon double bond, copolymer A is obtained by polymerizing the monomer component in the presence of an initiator used in radical polymerization or an initiator used in anionic polymerization. In particular, it is preferable to use an initiator used in radical polymerization, and azo compounds are more preferable.

[0107] (Polymerization 2) When the polymerizable reactive group of monomer m1 is a hydrolyzable silyl group, copolymer A is obtained by polymerizing the monomer component in the presence of an initiator used in cationic polymerization or an initiator used in anionic polymerization. In particular, it is preferable to use an initiator used in cationic polymerization. Organic acids, inorganic acids, and Lewis acids, which are initiators used in cationic polymerization, function as catalysts for hydrolysis reactions. Furthermore, the initiator is not limited to organic acids, inorganic acids, and Lewis acids, but can be any agent that catalyzes hydrolysis. For example, inorganic bases and organic bases may be used.

[0108] For example, if the polymerizable reactive group is a hydrolyzable silyl group represented by formula 9 above, the hydrolyzable silyl group is hydrolyzed and converted to a hydroxyl group, and then the hydroxyl group undergoes dehydration condensation to form a siloxane bond, and polymerization proceeds.

[0109] Polymerization 2 may be carried out by the sol-gel method (Method 1), or by coating an article with a solution containing monomer components and then allowing polymerization to proceed using moisture in the air (Method 2).

[0110] In Method 1, it is preferable to add the monomer component and, if necessary, the initiator to the aqueous medium described above, and then stir to carry out polymerization. The reaction solution may be heated if necessary.

[0111] In Method 2, a solution in which the monomer component is dissolved in the above-mentioned organic solvent or aqueous medium is coated onto an article by known methods such as application, impregnation, immersion, spraying, brushing, padding, sizing press, or rolling, and then the above-mentioned organic solvent or aqueous medium is dried. Drying may be carried out at room temperature or by heating, and heating is preferred. A steam-containing atmosphere is preferred for drying.

[0112] (Unit formation after polymerization) The units of copolymer A may be formed after polymerization. For example, a precursor compound of each monomer, monomer Z1 having a reactive group (Z1 group), may be polymerized in place of each monomer to obtain a precursor copolymer A', and then a compound Z2 having a reactive group (Z2 group) that can react with the reactive group (Z1 group) in unit Z1 of precursor copolymer A' may be reacted with the reactive group (Z1 group) in unit Z1 to form each unit.

[0113] There are no particular restrictions on the reactive group (Z1 group), but examples include hydroxyl groups, amino groups, isocyanate groups, mercapto groups, acid anhydride groups, and acyl chloride groups.

[0114] Examples of reactive groups (Z2) include reactive groups that can react with the above-mentioned reactive group (Z1). Examples include isocyanate groups, hydroxyl groups, amino groups, acid anhydride groups, and acyl chloride groups.

[0115] (Chain transfer agent) When polymerizing monomer components, a chain transfer agent that enables living radical polymerization may be used for further molecular weight control. The amount of chain transfer agent added is preferably 0 to 2 parts by mass, and more preferably 0 to 0.5 parts by mass, per 100 parts by mass of the total monomers.

[0116] A chain transfer agent having an anionic group may be used, a chain transfer agent without anionic groups may be used, or both may be used in combination. A single chain transfer agent may be used, or two or more may be used in combination.

[0117] Examples of chain transfer agents having anionic groups include, but are not limited to, 3,3'-dithio-dipropionic acid, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and thioglycolic acid. 3-mercaptopropionic acid having a carboxyl group is preferred.

[0118] Examples of chain transfer agents that do not have anionic groups include alkyl mercaptans such as tert-dodecyl mercaptan, n-dodecyl mercaptan, and stearyl mercaptan, aminoethanethiols, mercaptoethanol, 2,4-diphenyl-4-methyl-1-pentene, and carbon tetrachloride, but are not limited to these examples.

[0119] (Catalyst) A catalyst may be used to obtain copolymer A. There are no particular restrictions on the catalyst, but examples include tin compounds such as dibutyltin dilaurate (dibutyltin dilaurate (DBTDL)); and basic catalysts such as 1,4-diazabicyclo[2.2.2]octane (DABCO). These may be used individually or in combination of two or more. The amount of catalyst added is preferably 0 to 2 parts by mass, and more preferably 0 to 0.5 parts by mass, per 100 parts by mass of the total monomers.

[0120] <Mechanism of Action> Copolymer A, as described above, has units m1 and m2, and the proportion of units m2 is 30% by mass or more of the total constituent units. Copolymer A exhibits excellent oil repellency due to the presence of units m1, and excellent dirt removal properties due to the presence of units m2. Therefore, by treating with copolymer A, an article with excellent dirt removal properties and oil repellency can be obtained.

[0121] <<Anti-fouling oil-repellent composition>> The anti-fouling oil-repellent composition contains copolymer A. The anti-fouling oil-repellent composition may further contain a liquid medium. The anti-fouling oil-repellent composition may further contain other components other than copolymer A and the liquid medium as needed. The anti-fouling oil-repellent composition may be a solution or dispersion obtained by a method for producing copolymer A, or a liquid obtained by further diluting the above solution or dispersion.

[0122] Examples of liquid media include non-aqueous media and aqueous media, with aqueous media being preferred. When the liquid medium is a non-aqueous medium, the antifouling oil-repellent composition preferably comprises copolymer A and a non-aqueous medium, and is a polymer solution in which copolymer A is dissolved or dispersed in the non-aqueous medium, and may also contain an emulsifier. Typically, the amount of emulsifier in the polymer solution is 0.3 parts by mass or less per 100 parts by mass of copolymer A. When the liquid medium is an aqueous medium, the antifouling oil-repellent composition preferably is an aqueous dispersion containing copolymer A, an aqueous medium, and an emulsifier.

[0123] <Non-aqueous medium> The non-aqueous medium is a liquid medium that does not contain water or has a water content of 1% by mass or less relative to the total mass of the non-aqueous medium, and is typically an organic solvent. The water content relative to the total mass of the non-aqueous medium is preferably 0.8% by mass or less, and more preferably 0.5% by mass or less. The non-aqueous medium is not particularly limited as long as it can dissolve copolymer A, and examples include hydrocarbon organic solvents, ketone organic solvents, alcohol organic solvents, ester organic solvents, amide organic solvents, and ether organic solvents.

[0124] Examples of hydrocarbon-based organic solvents, ketone-based organic solvents, alcohol-based organic solvents, ester-based organic solvents, and ether-based organic solvents include those similar to the organic solvents exemplified as organic solvents used in the solution polymerization method for copolymer A, and may also be water-soluble organic solvents as described later.

[0125] There are no particular restrictions on the amide-based organic solvents, and examples include dimethylacetamide, 3-methoxydimethylpropanamide, 3-butoxydimethylpropanamide, and methylpyrrolidone. These may be used individually or in combination of two or more.

[0126] <Aqueous Media> Examples of aqueous media include water, or a mixture of water and a water-soluble organic solvent. A water-soluble organic solvent is an organic solvent that can be miscible with water in any proportion. As a water-soluble organic solvent, at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols, and aprotic polar solvents is preferred. Examples of alcohols include t-butanol and propylene glycol. Examples of ether alcohols include 3-methoxymethylbutanol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripylene glycol. Examples of aprotic polar solvents include N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (hereinafter referred to as "THF"), acetonitrile, and acetone. When the liquid medium is an aqueous medium, ether alcohols are preferred as the water-soluble organic solvent because they improve the compatibility between copolymer A and the aqueous medium and make it easier to form a uniform film on the surface of the article, and dipropylene glycol, tripylene glycol, and dipropylene glycol monomethyl ether are more preferred. These may be used individually or in combination of two or more. When the aqueous medium contains a water-soluble organic solvent, the content of the water-soluble organic solvent is preferably 1 to 80 parts by mass, and more preferably 10 to 60 parts by mass, per 100 parts by mass of water.

[0127] <Emulsifier> The emulsifier is a surfactant that has both hydrophilic and hydrophobic parts. Examples of emulsifiers include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, and amphoteric emulsifiers. Non-fluorinated emulsifiers that do not contain fluorine atoms are preferred. As for emulsifiers, from the viewpoint of excellent dispersion stability of the antifouling oil-repellent composition, the use of a nonionic emulsifier alone, a combination of a nonionic emulsifier and a cationic or amphoteric emulsifier, or the use of an anionic emulsifier alone is preferred, and the combination of a nonionic emulsifier and a cationic emulsifier is more preferred. The ratio of nonionic emulsifier to cationic emulsifier (nonionic emulsifier / cationic emulsifier) ​​is preferably 100 / 0 to 40 / 60 (mass ratio), and more preferably 97 / 3 to 40 / 60 (mass ratio). In certain combinations of nonionic and cationic emulsifiers, the total amount of emulsifiers per 100 parts by mass of copolymer A can be reduced to 5 parts by mass or less. Therefore, the adverse effect of emulsifiers on the oil repellency of water-resistant and oil-resistant paper, etc., using the antifouling and oil-repellent composition can be reduced.

[0128] As a nonionic emulsifier, surfactants s described in paragraphs

[0067] to

[0095] of Japanese Patent Application Publication No. 2009-215370 are used. １ ~s ６ Examples include surfactants. １ This is a polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, polyoxyalkylene monoalkapoleenyl ether, or polyoxyalkylene monopolyfluoroalkyl ether. Surfactant s １ Polyoxyethylene alkyl ether is preferred. Surfactants s ２ This refers to a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in its molecule. (Surfactant s) ２ As such, acetylene glycol ethylene oxide adducts are preferred. Surfactants s ３ This is a compound in which a polyoxyethylene chain and a polyoxyalkylene chain consisting of two or more oxyalkylene atoms with three or more carbon atoms linked together are connected, and both ends are hydroxyl groups. ３Ethylene oxide propylene oxide polymers are preferred as the emulsifier. Nonionic emulsifiers may be used alone or in combination of two or more.

[0129] As cationic emulsifiers, surfactants s described in paragraphs

[0096] to

[0100] of Japanese Patent Application Publication No. 2009-215370 ７ Examples include surfactants. ７ It is a substituted ammonium salt type cationic emulsifier.

[0130] Surfactants ７ Preferably, the ammonium salt is one in which one or more hydrogen atoms bonded to the nitrogen atom are substituted with an alkyl group, an alkenyl group, or a polyoxyalkylene chain having a hydroxyl group at the end, as shown in the following formula s ７１ Compounds represented by s ７１ It is more preferable. [(R ２１ ) ４ N ＋ ]・X － formula s ７１

[0131] formula s ７１ Medium, R ２１ These are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a polyoxyalkylene chain with a hydroxyl group at the end. ２１ These may be the same or different, but the four R's ２１ It is not a hydrogen atom at the same time. X － X is the counterion. － Preferably, chloride ions, ethyl sulfate ions, and acetate ions are used.

[0132] compound s ７１ Examples include monostearyltrimethylammonium chloride, monostearyldimethylmonoethylammonium ethyl sulfate, mono(stearyl)monomethyldi(polyethylene glycol)ammonium chloride, di(tallow alkyl)dimethylammonium chloride, and dimethylmonococonutamine acetate. Cationic emulsifiers may be used individually or in combination of two or more.

[0133] As an amphoteric emulsifier, surfactants s described in paragraphs

[0101] to

[0102] of Japanese Patent Application Publication No. 2009-215370 ８ Examples include surfactants. ８ One type may be used, or two or more types may be used in combination. Surfactants s ８ These are alanine, imidazolinium betaine, amide betaine, or betaine acetate.

[0134] <Other Components> Other components may be added to the solution or dispersion obtained by the synthesis reaction of copolymer A, or to a solution obtained by further diluting the above solution or dispersion. Other components include nonfluorinated polymers other than copolymer A, nonfluorinated water- and oil-repellent agents, water-soluble polymer resins (e.g., hydrophilic polyesters and their derivatives, hydrophilic polyethylene glycols and their derivatives, hydrophilic polyamines and their derivatives, hydrophilic polyvinyl alcohols and their derivatives), crosslinking agents, penetrating agents (e.g., nonionic surfactants with a symmetrical structure having an acetylene group in the center, such as the Dispanol® series manufactured by NOF Corporation), colloidal silica (e.g., the Snowtex® series manufactured by Nissan Chemical Corporation, the Adelheid series manufactured by ADEKA Corporation) Examples of these include defoaming agents (e.g., Orfin® series manufactured by Nisshin Chemical Co., Ltd., FS Antifoam series manufactured by Toray Dow Corning Co., Ltd.), film-forming aids, insecticides, fungicides, preservatives, flame retardants, antistatic agents (e.g., Directol series manufactured by Meisei Chemical Co., Ltd.), wrinkle inhibitors, softeners (e.g., silicone emulsion, polyethylene wax emulsion), pH adjusters (e.g., diethanolamine, triethanolamine, acetic acid, citric acid), fatty acid amides (e.g., those described in Japanese Patent Publication No. 2014-98082), acrylic resins, and urethane resins. Two or more of these may be used in combination.

[0135] Other components to be added to a solution obtained by further diluting the above solution or dispersion for processing articles include, as concomitant agents for external additive processing described later, paper strength enhancers (various starches, resins, etc.), sizing agents, penetrating agents, defoaming agents, chelating agents, dyes, pigments, binders, acids, alkalis, alginates, and aluminum sulfate. As concomitant agents for internal additive processing described later, examples include coagulants, yield enhancers, sizing agents, paper strength enhancers, pigments, dyes, and pH adjusters. Other components may be used individually or in combination of two or more.

[0136] When an antifouling and oil-repellent composition contains a crosslinking agent, its adhesion to articles tends to improve. Examples of crosslinking agents include polyfunctional acrylic crosslinking agents, isocyanate crosslinking agents, methylol crosslinking agents, carbodiimide crosslinking agents, crosslinking systems using the enthiol reaction by adding polyfunctional thiols, and oxazoline crosslinking agents.

[0137] Examples of isocyanate crosslinking agents include aromatic blocked-type isocyanate crosslinking agents, aliphatic blocked-type isocyanate crosslinking agents, aromatic non-blocked-type isocyanate crosslinking agents, and aliphatic non-blocked-type isocyanate crosslinking agents. The isocyanate crosslinking agent is preferably an aqueous dispersion type emulsified with a surfactant, or a self-aqueous dispersion type having hydrophilic groups.

[0138] Examples of methylol-based crosslinking agents include condensates or pre-condensates of urea or melamine with formaldehyde, methylol-dihydroxyethylene-urea and its derivatives, methylol-ethylene-urea, methylol-propylene-urea, methylol-triazone, condensates of dicyandiamide-formaldehyde, methylol-carbamate, methylol-(meth)acrylamide, and polymers thereof.

[0139] Carbodiimide-based crosslinking agents are polymers having carbodiimide groups in their molecules and exhibit excellent reactivity with carboxyl groups, amino groups, and active hydrogen groups on the surface of articles. Oxazoline-based crosslinking agents are polymers having oxazoline groups in their molecules and exhibit excellent reactivity with carboxyl groups on the surface of articles.

[0140] Other crosslinking agents include divinyl sulfone, polyamides and their cationic derivatives, polyamines and their cationic derivatives, epoxy derivatives such as diglycidylglycerol, halide derivatives such as (epoxy-2,3-propyl)trimethylammonium chloride and N-methyl-N-(epoxy-2,3-propyl)morpholinium chloride, pyridinium salts of chloromethyl ether of ethylene glycol, polyamine-polyamide-epicrohydrin resins, polyvinyl alcohol or its derivatives, polyacrylamide or its derivatives, and glyoxal resin-based anti-wrinkle agents.

[0141] When an antifouling and oil-repellent composition contains a methylol-based crosslinking agent or a glyoxal resin-based anti-wrinkle agent, it is preferable to include a catalyst as an additive. Examples of preferred catalysts include inorganic amine salts and organic amine salts. An example of an inorganic amine salt is ammonium chloride. Examples of organic amine salts include amino alcohol hydrochloride and semicarbazide hydrochloride. Examples of amino alcohol hydrochloride include monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanolamine hydrochloride, and 2-amino-2-methylpropanol hydrochloride.

[0142] <Proportion of each component> When the antifouling oil-repellent composition contains a liquid medium, the amount of liquid medium can be appropriately selected according to the desired solid content concentration of the antifouling oil-repellent composition. The solid content concentration of the antifouling oil-repellent composition is preferably 5 to 80% by mass, more preferably 10 to 50% by mass, and even more preferably 10 to 40% by mass immediately after the production of the antifouling oil-repellent composition. When the antifouling oil-repellent composition is used for coating articles, the solid content concentration is preferably 0.1 to 80% by mass, more preferably 0.1 to 50% by mass, and even more preferably 0.1 to 30% by mass. The content of copolymer A relative to the total mass of the antifouling oil-repellent composition is preferably 0.1 to 80% by mass, more preferably 0.1 to 50% by mass, and even more preferably 0.1 to 30% by mass.

[0143] The fluorine atom content relative to the total mass of the antifouling oil-repellent composition is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. Most preferably, the antifouling oil-repellent composition is non-fluorinated and does not contain fluorine atoms. The fluorine atom content relative to the total mass of the antifouling oil-repellent composition can be measured by combustion ion chromatography or the like.

[0144] Antifouling and oil-repellent compositions are widely used in coating applications. The coating method is not particularly limited. Examples include treating the article by known methods such as application, impregnation, immersion, spraying, brushing, padding, sizing press, and rolling, followed by drying. The amount of solids in the antifouling and oil-repellent composition to be applied to the article is not particularly limited, but in the case of textiles, 0.1 to 5 g per 100 g of textile is preferred, 0.1 to 3 g is more preferred, and 0.1 to 1 g is even more preferred. The content of copolymer A in the antifouling and oil-repellent composition to be applied to the article is not particularly limited, but in the case of textiles, 0.01 to 5 g per 100 g of textile is preferred, 0.02 to 3 g is more preferred, and 0.03 to 1 g is even more preferred. Drying may be performed at room temperature or by heating, and heating is preferred. When heating, the heating temperature is preferably 90 to 200°C. Furthermore, if the antifouling and oil-repellent composition contains a crosslinking agent, it is preferable to heat it to a temperature above the crosslinking temperature of the crosslinking agent and cure it if necessary.

[0145] <Use of Antifouling and Oil-Repellent Composition> The antifouling and oil-repellent composition is suitably used to impart antifouling and oil-repellent properties to textiles, glass, paper, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded products, porous resins, porous fibrous materials, etc. The antifouling and oil-repellent composition of this embodiment is preferably for textiles or paper, and more preferably for textiles. The antifouling and oil-repellent composition can be used as a water repellent, oil repellent, water-repellent and oil-repellent agent, water-resistant agent, oil-resistant agent, water-resistant and oil-resistant agent, antifouling agent, oleophobic agent, etc. It can also be used as a moisture-proofing agent, water-slip agent, mold release agent, release agent, resin adhesion inhibitor, biological adhesion inhibitor, etc.

[0146] ≪Articles≫ This embodiment includes articles treated with copolymer A. Examples of articles include fibers (textile fabrics (woven fabrics, knitted fabrics, nonwoven fabrics, napped fabrics, etc.) and textile products equipped with textile fabrics (clothing such as ski wear, rainwear, coats, blousons, windbreakers, down jackets, sportswear, work clothes, uniforms, protective clothing, backpacks, bags, tents, etc.)), glass, paper (including pulp), wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded articles, porous resins, and porous fibrous materials. Porous resins are used, for example, as filters. Examples of porous resin materials include polypropylene, polyethylene terephthalate, and polytetrafluoroethylene. Examples of porous fibrous materials include glass fibers, cellulose nanofibers, carbon fibers, and cellulose acetate fibers.

[0147] As for the articles, fibers (including fiber fabrics and fiber products equipped with fiber fabrics) and paper are preferred, with fibers being preferred, in terms of exhibiting good oil repellency and stain removal properties. The type of fiber is not particularly limited, but examples include natural fibers such as cotton, wool, silk or cellulose, chemical fibers such as polyester, polyamide, acrylic, aramid, rayon, lyocell, and fibers obtained using multiple of these fibers. Examples of fibers in nonwoven fabrics include polyethylene, polypropylene, polyolefin, polyethylene terephthalate, polytetrafluoroethylene, glass and rayon. The thickness of the fiber fabric is not particularly limited, but is 10 μm to 5 cm.

[0148] <Water and Oil Resistant Paper> Water and oil resistant paper may be obtained by treating pulp or paper with copolymer A. Since water and oil resistant paper is made by treating pulp or paper with copolymer A, it has excellent practical oil resistance. Water and oil resistant paper may be obtained by the external additive process described below, or by the internal additive process.

[0149] External addition method: A method of applying or impregnating a paper substrate with an antifouling and oil-repellent composition containing copolymer A. Internal addition method: A method of papermaking using a pulp slurry containing copolymer A.

[0150] In both external and internal additive processes, the antifouling and oil-repellent composition may be diluted with water or an aqueous medium before use. The solid content concentration of the antifouling and oil-repellent composition used in the method for manufacturing water-resistant and oil-resistant paper is preferably 10 to 30% by mass, and more preferably 20 to 25% by mass.

[0151] <Performance of the Article> Preferred upper limits for the water contact angle of glass treated with the antifouling and oil-repellent composition of this embodiment are, for example, 80°, 50°, 30°, 28°, 26°, 25°, 23°, and 21°. The water contact angle is measured by the method described in the examples below. Preferred lower limits for the n-hexadecane contact angle of glass treated with the antifouling and oil-repellent composition of this embodiment are, for example, 45°, 50°, 51°, 52°, 53°, 54°, 55°, 56°, and 57°. The n-hexadecane contact angle is measured by the method described in the examples below.

[0152] For fibers (especially polyester fibers) treated with the anti-fouling oil-repellent composition of this embodiment, the oil repellency test grade according to the AATCC standard-TM118 method is preferably 2 or higher, and more preferably 3 or higher. The oil repellency test is carried out by the method described in the examples below. For fibers (especially polyester fibers) treated with the anti-fouling oil-repellent composition of this embodiment, the stain removal performance grade is preferably 3 or higher, and more preferably 4 or higher. The stain removal performance test is carried out by the method described in the examples below.

[0153] The embodiments will be described in more detail below with reference to examples, but the present invention is not limited to the following description. Examples 1 to 5 and 8 to 16 are examples, and Examples 6 and 7 are comparative examples.

[0154] <Measurement and Evaluation> The measurement and evaluation methods are as follows.

[0155] <Percentage of Monomer Units> The composition of the polymer (the percentage of each monomer unit relative to the total number of units constituting the polymer) was calculated based on the amount of monomer components used. GPC measurements were performed on the solutions or dispersions obtained by polymerization in each example, and it was confirmed that there were no peaks originating from monomers. Therefore, the conversion rate of each monomer component to the polymer was 90% or higher, and the percentage of each unit could be calculated based on the amount of each monomer component used.

[0156] <Water Contact Angle, n-Hexadecane Contact Angle> Diluted solutions were obtained by diluting the polymer of each example with MEK to a solid content concentration of 2% by mass. After ultrasonic cleaning in ethanol for 30 seconds, the samples were spun onto a glass substrate (AGC, dimensions 50 mm x 50 mm x 0.7 mm) that had been UV / ozone cleaned for 5 minutes (device: PL7-200, manufactured by Sen Engineering Co., Ltd.) using a spinner (Mikasa Corporation, IH-DX2) (rotation speed 2000 rpm, 30 seconds). The samples were then dried on a hot plate set to 80°C for 10 minutes to obtain the measurement samples. 2 μL of deionized water or n-hexadecane was added to the surface of the measurement samples, and the contact angle after 1 minute was measured using a contact angle measuring device (Kyowa Interface Science Co., Ltd., DM-500). Measurements were taken at five different locations on the surface, and the average value was calculated. The θ / 2 method was used to calculate the contact angle. The water contact angle was 50 [deg. The following is preferable. The n-hexadecane contact angle is preferably 45 [deg.] or greater.

[0157] <Preparation of Test Fabrics> 150 g of the treatment solution for each example was immersed in tropical cloth made of undyed polyester. Then, it was squeezed with a mangle to achieve a wet pickup of 80-90%. Next, it was dried at 110°C for 90 seconds and then cured at 170°C for 60 seconds to obtain the test fabrics.

[0158] <Oil Repellency> The oil repellency of the test fabric was evaluated using the AATCC standard-TM118 method. The evaluation results are shown in Table 1 as oil repellency grades. This oil repellency grade is based on the wettability of the fabric with eight types of hydrocarbon solvents (test solutions) with different surface tensions. A higher oil repellency grade indicates higher oil repellency. A grade of 2 or higher is preferable.

[0159]

[0160] <Dirt Removal Performance> A test cloth was spread on absorbent paper laid horizontally. Five drops (approximately 0.2 ml) of a dirt solution, made by adding 0.1% by mass of carbon black to used engine oil, were dropped onto the cloth. A polyethylene sheet was placed over the test cloth with the dirt solution. A 60 g weight was then placed on top of the polyethylene sheet. After one hour, the weight and polyethylene sheet were removed. Excess dirt solution was wiped off with filter paper, and the test cloth was left at room temperature for 20 minutes before being washed. The test cloth after washing was visually inspected and graded according to the standards shown in Table 2. A higher grade indicates better dirt removal performance. A grade of 3 or higher is preferable.

[0161]

[0162] ≪Materials≫ The materials used in each example and their abbreviations are listed below.

[0163] <Monomer m1> The monomers m1-1 (Tokyo Chemical Co., Ltd. product) and m1-2 shown below were used.

[0164]

[0165]

[0166] Monomer m1-1 is X in Equation 1. １ A is a methacryloyloxy group, １ is a trimethylene group, B １ The compound is a group represented by formula 51. Monomer m1-2 is X in formula 1. １ A is a methacryloyloxy group, １ is a trimethylene group, B １ The compound is a group represented by formula 61. n is 2 on average.

[0167] (Synthesis of monomer m1-2) Monomer m1-2 was synthesized via the reaction pathway shown below.

[0168]

[0169] 5.00 g of hydroxytrimethylsilane and 100 mL of THF were placed in a 300 mL four-necked flask. After cooling to 0°C, 33 mL of n-butyllithium (in a 1.6 M hexane solution) was added and the mixture was stirred for 30 minutes. After raising the temperature to room temperature, 25 mL of a THF solution containing 8.28 g of hexamethylcyclotrisiloxane was added and the mixture was stirred for 16 hours. Subsequently, 12.24 g of 3-(chlorodimethylsilyl)propyl methacrylate was added and the mixture was stirred for 3 hours. After the reaction was complete, water was added, the mixture was extracted with ethyl acetate, washed sequentially with water and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain the crude product as a colorless liquid. This was purified by silica gel column chromatography (hexane / ethyl acetate = 99 / 1) to obtain 14.8 g of monomer m1-2 as a colorless transparent oil. NMR analysis of the obtained monomer m1-2 showed that the average value of n in the formula was 2. Furthermore, when the molecular weight was measured using GPC (polymethyl methacrylate equivalent molecular weight), the results were Mn 625 and Mw 691. １ H NMR (400 MHz, CDCl ３ )δ 6.10 (d, J=0.7Hz, 1H), 5.54 (t, J=1.5Hz, 1H), 4.10 (t, J=6.9Hz, 2H), 1 .95 (s, 3H), 1.77-1.64 (m, 2H), 0.61-0.54 (m, 2H), 0.12-0.02 (m, 27H).

[0170] <Comparative monomer m1> StA: Stearyl acrylate

[0171] <Monomer m2> PME200:CH ２ = C(CH ３ )-C(=O)O-(C ２ H ４ O) ｑ１ -CH ３ (NOF Corporation product, Bremmer PME-200, q １ ≒4) PME400:CH ２ = C(CH ３ )-C(=O)O-(C ２ H ４ O) ｑ１ -CH ３ (NOF Corporation product, Bremmer PME-400, q １ ≒9) PE350:CH ２ = C(CH３ )-C(=O)O-(C ２ H ４ O) ｑ１ -H (NOF Corporation product, Bremmer PE-350, q １ ≒8) 55PET800:CH ２ = C(CH ３ )-C(=O)O-[(C ２ H ４ O) ｑ１ (C ４ H ８ O) ｑ２ ]-H (Nippon Oil & Fats Co., Ltd. product, Bremmer 55PET-800, q １ ≈ 10, q ２ ≒5) AE400:CH ２ =CH-C(=O)O-(C ２ H ４ O) ｑ１ -H (NOF Corporation product, Bremmer AE-400, q １ ≒10)

[0172] <Comparative monomer m2> PP800:CH ２ = C(CH ３ )C(O)O-(C ３ H ６ O) ｃ -H (NOF Corporation product, Bremmer PP-800, c≈13)

[0173] <Monomer m3> DMAEMA: Dimethylaminoethyl methacrylate

[0174] <Chain transfer agent> Mercaptopropionic acid: 3-mercaptopropionic acid DoSH: n-dodecyl mercaptan

[0175] <Initiators> AIBN: 2,2'-Azobisisobutyronitrile (product of Fujifilm Wako Pure Chemical Industries, Ltd.) ACP: 4,4'-Azobis(4-cyanovaleric acid)

[0176] <Liquid media> MEK: Methyl ethyl ketone water: Ion-exchanged water

[0177] ≪Example 1≫ 30 g of monomer m1-1, 20 g of PME200, and 100 g of MEK were charged into a 200 ml glass reactor and mixed uniformly. 0.5 g of AIBN was then added as a polymerization initiator, and the top plate was closed. The inside of the glass reactor was then purged with nitrogen, the temperature was raised to 60°C, and the polymerization reaction was carried out for 10 hours to obtain a non-fluorine copolymer.

[0178] Examples 2-10: Non-fluorinated copolymers for each example were obtained under the same conditions as in Example 1, except that the monomer types and composition ratios were changed as shown in Table 3. The compositions shown in Table 3 are the mass ratios when the total amount of monomers is 100 parts by mass.

[0179]

[0180] In Examples 1-5 and 8-10, the water contact angle was lower than in Examples 6 and 7, indicating good hydrophilicity. This is thought to be because hydrophilic groups are easily oriented on the surface of the article, making it easier for dirt to be removed by wiping or washing once it has adhered, resulting in good dirt removal properties. In addition, in Examples 1-5 and 8-10, the n-hexadecane contact angle was higher than in Examples 6 and 7, indicating good oil repellency.

[0181] ≪Example 11≫ In a 200 ml glass reactor, 27.5 g of monomer m1-1, 14.5 g of PME400, 6.5 g of 55PET800, 0.25 g of mercaptopropionic acid, and 100 g of MEK were charged and mixed uniformly. 0.5 g of ACP was then added as a polymerization initiator, and the top plate was closed. The glass reactor was then purged with nitrogen, the temperature was raised to 60°C, and the polymerization reaction was carried out for 10 hours to obtain a non-fluorine copolymer. To 100 g of the obtained polymer solution, 132.7 g of water (400 parts by mass relative to the total mass of monomer components) and 0.57 g of acetic acid (1.5 times the molar equivalent of DMAEMA) were added and mixed to perform amine chlorination treatment. Subsequently, MEK was removed at 60°C under reduced pressure to obtain a pale yellow transparent aqueous dispersion. Subsequently, water was added to obtain an aqueous dispersion with a solid content concentration of 20% by mass. The aqueous dispersion was measured by capillary gas chromatography and confirmed that the MEK content was 1% by mass or less. The obtained aqueous dispersion and Meikanate TP-10 (a product of Meisei Chemical Industry Co., Ltd., a blocked isocyanate-based crosslinking agent) were added to ion-exchanged water. A treatment solution (anti-fouling oil-repellent composition) was obtained with a solid content concentration of 2% by mass of the non-fluorine copolymer and a crosslinking agent concentration of 1.5% by mass.

[0182] Examples 12-16: Non-fluorinated copolymers and treatment solutions for each example were obtained under the same conditions as in Example 11, except that the composition of monomer components, the type of chain transfer agent, and the initiator were changed as shown in Table 4. The compositions shown in Table 4 are the mass ratios when the total amount of monomer components is 100 parts by mass.

[0183]

[0184] In Examples 11-16, excellent stain removal and oil repellency were also imparted to the test cloth.

[0185] According to one embodiment, a non-fluorine copolymer can be obtained that yields an article with excellent stain removal properties and oil repellency, an anti-fouling oil-repellent composition containing the non-fluorine copolymer, and an article with excellent stain removal properties and oil repellency can be provided.

[0186] This application claims priority based on Japanese Patent Application No. 2025-13796, filed on 30 January 2025, and the entire contents of the said Japanese application are incorporated herein by reference.

Claims

1. A non-fluorine copolymer having a unit based on the monomer represented by the following formula 1 and a unit based on the monomer represented by the following formula 2, wherein the proportion of the unit based on the monomer represented by the following formula 2 is 30% by mass or more of all the constituent units. X １ -A １ -B １ ... Formula 1 In Formula 1, X １ is a monovalent polymerizable reactive group, A １ is a divalent organic group, B １ is a monovalent organic group having at least one trialkylsilyl group. CH ２ =CR １ -G-[(C ２ H ４ O) ｑ１ (C ４ H ８ O) ｑ２ -R ２ ... Formula 2 In Formula 2, R １ is a hydrogen atom or a methyl group, G is C(=O)O-(CH ２ ) ｒ - or -C(=O)O-(CH ２ ) ｔ -NH C(=O)O-, r is an integer from 0 to 4, t is an integer from 1 to 4, R ２ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a (meth)acryloyl group or a glycidyl group, q １ is an integer from 3 to 100, q ２ is an integer from 0 to 50.

2. The non-fluorinated copolymer according to claim 1, further comprising either one or both of the units based on the monomer represented by formula 3 and the units based on the monomer represented by formula 4 below. ２ =CR ３ -M １ -Q １ -NR ４ R ５ ...Formula 3 CH ２ =CR ６ -M ２ -Q ２ -N(O)R ７ R ８ ...Equation 4 In Equations 3 and 4, R ３ and R ６ Each is independently a hydrogen atom or a methyl group, M １ and M ２ Each of these is independently -C(=O)O- or -C(=O)NH-, and Q １ and Q ２ Each of these is independently an alkylene group having 2 to 4 carbon atoms or an alkylene group having 2 to 3 carbon atoms in which some or all of the hydrogen atoms are replaced by hydroxyl groups, R ４ , R ５ , R ７ and R ８ Each of these is independently a benzyl group, a C1-C8 alkyl group, and a C2-C3 alkyl group in which some of the hydrogen atoms are replaced by hydroxyl groups, R ４ , R ５ The nitrogen atom may form a piperidino group or a pyrrolidinyl group, R ７ , R ８ The oxygen and nitrogen atoms may form morpholino groups.

3. The non-fluorinated copolymer according to claim 1, wherein the proportion of units based on the monomer represented by formula 2 is 35% by mass or more of the total constituent units of the non-fluorinated copolymer.

4. In the above equation 2, q １ is an integer between 3 and 50, and q ２ The non-fluorine copolymer according to claim 1, wherein is an integer from 1 to 50.

5. Having two or more units based on monomers represented by formula 2, the two or more units are q １ is 3 to 50 and the aforementioned q ２ A unit based on a monomer in which q is 0, and the q １ is 3 to 50 and the aforementioned q ２ The non-fluorine copolymer according to claim 1, having at least units based on monomers where is 1 to 50.

6. In the non-fluorine copolymer, the q １ is 3 to 50 and the aforementioned q ２ For units based on monomers where q is 0, １ is 3 to 50 and the aforementioned q ２ The non-fluorine copolymer according to claim 5, wherein the mass ratio of units based on monomers, where is 1 to 50, is 0.1 to 2.

0.

7. The non-fluorinated copolymer according to claim 1, having an anionic group at the end of the main chain.

8. The non-fluorinated copolymer according to claim 7, wherein the anionic group is a carboxyl group.

9. The aforementioned X １ is a (meth)acryloyloxy group or a hydrolyzable silyl group, and the B １ The non-fluorine copolymer according to claim 1, wherein the silicon number is 10 or less.

10. The B １ is a monovalent organic group represented by the following formula 5 or a monovalent organic group represented by the following formula 6. The non-fluorine copolymer according to claim 1. Ａ１ * - Si(OSiR １５ ３ ) ３－ｂ R １６ ｂ ・・・ Formula 5 Ａ１ * - SiR １７ ２ (OSiR １８ ２ ) ｎ OSiR １９ ３ ・・・ Formula 6 In Formula 5, b is an integer of 0 to 2, and R １５ are each independently - OSiR １５１ ３ , - R １５２ - Si(OSiR １５１ ３ ) ３－ｃ R １５３ ｃ , or a linear or branched alkyl group having 1 to 6 carbon atoms, and R １５１ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, R １５２ is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, and R １５３ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, c is an integer of 0 to 2, and R １６ / / There seems to be a repetition here in the original, and it's not clear if it's a mistake. Translated as is. are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, Ａ１＊ - is a bond with A １ . In Formula 6, R １７ , R １８ and R １９ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, n is an integer of 0 or more, Ａ１＊ - is a bond with A １ .

11. The B １ is a monovalent organic group represented by the following formula 51, a monovalent organic group represented by the following formula 52, or a monovalent organic group represented by the following formula 61: The non-fluorine copolymer according to claim 1. In formula 51, formula 52, and formula 61, Ａ１ *− is a bond with A １ and in formula 61, n is an integer of 0 to 3.

12. The non-fluorinated copolymer according to claim 1, wherein the proportion of units based on the monomer represented by formula 1 is 25% by mass or more of the total constituent units of the non-fluorinated copolymer.

13. An antifouling and oil-repellent composition comprising a non-fluorine copolymer according to any one of claims 1 to 12.

14. The stain-resistant and oil-repellent composition according to claim 13, for use with textiles.

15. A textile article treated with the antifouling and oil-repellent composition according to claim 13.

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