Oil repellent composition, article, and method for producing oil repellent composition

Abstract

This oil repellent composition contains at least one of the following copolymer A and copolymer B.　Copolymer A: A copolymer which includes a unit based on a monomer represented by formula 1 and a unit based on a nonionic monomer that has a solubility of 1 g / 100 mL or more with respect to water at 20°C.　Copolymer B: A copolymer which includes a unit based on a monomer represented by formula 1 and units based on ionic monomers each having an ion-donating group, and in which the units based on ionic monomers include a unit based on a monomer having a cation-donating group and a unit based on a monomer having an anion-donating group.　In formula 1, X1 represents a monovalent polymerizable reactive group, A1 represents a divalent organic group, and B1 represents a monovalent organic group having at least one trialkylsilyl group.　Formula 1: X1-A1-B1

Description

Oil-repellent composition, article, and method for producing oil-repellent composition

[0001] The present disclosure relates to an oil-repellent composition, an article, and a method for producing an oil-repellent composition. This application claims priority based on Japanese Patent Application No. 2024-213190 filed in Japan on December 6, 2024, and US Patent Application No. 63 / 888,600 filed in the United States on September 26, 2025, the contents of which are incorporated herein by reference.

[0002] As a method for imparting oil repellency to the surface of articles such as paper and textile products, a method of treating an article with a water and oil repellent composition containing a fluoropolymer is known.

[0003] International Publication No. 2007 / 034818

[0004] However, the fluoropolymer used in the above method is a concern in terms of high environmental impact. Therefore, an oil-repellent composition containing a non-fluoropolymer that can impart sufficient oil repellency to the surface of an article and has a low environmental impact is required. The present disclosure provides an oil-repellent composition, an article, and a method for producing an oil-repellent composition that can obtain an article with excellent oil repellency.

[0005] The present disclosure has the following aspects. [1] An oil-repellent composition containing at least one of the following copolymer A and copolymer B. Copolymer A: A copolymer containing a unit based on a monomer represented by the following formula 1 and a unit based on a nonionic monomer having a solubility in water at 20 °C of 1 g / 100 mL or more. Copolymer B: A copolymer containing a unit based on a monomer represented by the following formula 1 and a unit based on an ionic monomer having an ion-donating group, and the unit based on the ionic monomer contains a unit based on a monomer having a cation-donating group and a unit based on a monomer having an anion-donating group. X １ -A １ -B １ ... (Formula 1) In the above formula 1, X １ is a monovalent polymerizable reactive group, A １ is a divalent organic group, and B １ is a monovalent organic group represented by the following formula 3 or a monovalent organic group represented by the following formula 4. Ａ１＊ -Si(OSiR １５ ３) ３－ｂ R １６ ｂ ... (Equation 3) In Equation 3 above, R 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, R 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 independently a linear or branched alkyl group having 1 to 6 carbon atoms, and R １６ Each of these is independently a linear or branched alkyl group having 1 to 6 carbon atoms, b is an integer from 0 to 2, and c is an integer from 0 to 2. Ａ１＊ - is A １ This is a combination of the two. Ａ１＊ -SiR １７ ２ (OSiR １８ ２ ) ｎ OSiR １９ ３ ... (Equation 4) In Equation 4 above, R １７ , R １８ and R １９ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms, and n is an integer from 0 to 10. Ａ１＊ - is A １ [2] The oil repellent composition according to [1], wherein the content of units based on the monomer represented by formula 1 is more than 25% by mass of the total units constituting the copolymer A. [3] The copolymer A and an aqueous medium, wherein B １The oil-repellent composition according to [2], wherein is a monovalent organic group represented by formula 3, and the copolymer A further comprises units based on an ionic monomer having a cation donor group, and satisfies either or both of the following requirements (1a) and (2a): (1a): The content of the units based on the nonionic monomer is greater than 20% by mass relative to the total units constituting the copolymer A. (2a): The nonionic monomer does not have a polyoxyalkylene chain, and the content of the units based on the nonionic monomer is greater than 10% by mass relative to the total units constituting the copolymer A. [4] The copolymer A and an aqueous medium, wherein the copolymer A further comprises units based on an ionic monomer having a cation donor group, and the content ratio (mol%) of the units based on the monomer represented by formula 1 relative to the total units constituting the copolymer A is M Ａ１ The content percentage (mol%) of the unit based on the nonionic monomer is M Ａ２ When that happens, M Ａ２ / M Ａ１ The oil-repellent composition according to [2], wherein is 1.2 to 5.2. [5] The oil-repellent composition according to [3], further comprising an acid, wherein at least a portion of the cation-donating group is ionized by the acid. [6] The oil-repellent composition according to [5], wherein the pH at 25°C is less than 7.0. [7] The oil-repellent composition according to [2], comprising the copolymer A and an aqueous medium, wherein the copolymer A further comprises units based on an ionic monomer having an anion-donating group, the content of the units based on the nonionic monomer is more than 40% by mass of the total units constituting the copolymer A, and the nonionic monomer does not have a polyoxyalkylene chain. [8] The B １ The oil-repellent composition according to [7], wherein is a monovalent organic group represented by formula 3. [9] The copolymer A and an aqueous medium, wherein the copolymer A further comprises units based on an ionic monomer having an anion donating group, and the content ratio (mol%) of units based on the monomer represented by formula 1 to the total units constituting the copolymer A is M Ａ１ The content percentage (mol%) of the unit based on the nonionic monomer is M Ａ２ When that happens, M Ａ２ / M Ａ１ The oil-repellent composition according to [2], wherein the ratio is 2.3 or higher.

[10] The M Ａ２ / M Ａ１ The oil-repellent composition according to [9], wherein is 5.3 or less.

[11] comprising the copolymer A and an aqueous medium, wherein the copolymer A further comprises units based on an ionic monomer having an anion donating group, and the content ratio (mol%) of the units based on the nonionic monomer to the total units constituting the copolymer A is M Ａ２ The content ratio (mol%) of the unit based on the anionic monomer is M Ａ３１ When that happens, M Ａ２ / M Ａ３１ The oil-repellent composition according to [2], wherein the ratio is 3.5 or higher.

[12] The oil-repellent composition according to [7], further comprising a base, wherein at least a portion of the anion-donating group is ionized by the base.

[13] The oil-repellent composition according to

[12] , wherein the pH at 25°C is greater than 7.0.

[14] The oil-repellent composition according to [2], comprising the copolymer B, wherein the copolymer B further comprises units based on a nonionic monomer having a solubility in water at 20°C of 1 g / 100 mL or more.

[15] The oil-repellent composition according to

[14] , satisfying one or more of the following requirements (3a) to (5a): (3a) the B １ (1) is a monovalent organic group represented by formula 3. (4a) The content of units based on the nonionic monomer is more than 20% by mass relative to the total units constituting the copolymer B. (5a) The nonionic monomer does not have a polyoxyalkylene chain.

[16] The content ratio (by mass) of units based on the monomer having the anion donor group relative to the total units constituting the copolymer B is W Ｂ３１ The content ratio (mass%) of the unit based on the monomer having the cation donor group is W Ｂ３２ When that happens, W Ｂ３２ / W Ｂ３１ The oil-repellent composition according to

[14] , wherein W is greater than 2.0.

[17] The content ratio (mass%) of the unit based on the nonionic monomer relative to the total units constituting the copolymer B is W Ｂ２ The content ratio (mass%) of the unit based on the cationic monomer is W Ａ３２When that happens, W Ｂ２ / W Ｂ３２ The oil-repellent composition according to

[14] , wherein is 2.8 to 9.5.

[18] The oil-repellent composition according to

[14] , further comprising an acid, wherein at least a portion of the cation donor group is ionized by the acid.

[19] The content ratio (mass%) of units based on the monomer having the anion donor group relative to the total units constituting the copolymer B is W Ｂ３１ The content ratio (mass%) of the unit based on the monomer having the cation donor group is W Ｂ３２ When that happens, W Ｂ３２ / W Ｂ３１ The oil-repellent composition according to

[14] , wherein W is greater than 0 and less than or equal to 2.0.

[20] The W Ｂ３２ / W Ｂ３１ The oil-repellent composition according to

[19] , wherein the ratio is less than 1.0.

[21] The oil-repellent composition according to

[20] , further comprising a base, wherein at least a portion of the anion-donating group is ionized by the base.

[22] The oil-repellent composition according to [1], comprising copolymer A, further comprising a unit based on an ionic monomer having a cation-donating group, or comprising copolymer B, wherein the ionic monomer having a cation-donating group in copolymer A and copolymer B has a heterocycle.

[23] The oil-repellent composition according to

[22] , further comprising polyvinyl alcohol.

[24] The oil-repellent composition according to [1], wherein the nonionic unit is a unit based on a monomer represented by the following formula 2. CH ２ = C(R ２１ ) - A ２ ... (Equation 2) In Equation 2 above, R ２１ is a hydrogen atom, a halogen atom, or a methyl group, A ２ The following equation A ２１ A ２２ Or A ２３ This is the group represented by -C(O)-O-B ２１ ...(Formula A ２１ ) -C(O)-N(R ２２ )-B ２２ ...(Formula A ２２ ) -N(R ２３ )-C(O)-B ２３ ...(Formula A２３ ), in the formula A ２１ , B ２１ is a monovalent group that does not contain a hydrophobic group having 8 or more carbon atoms, and is (1) a group in which one or more bonds selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, and an ester bond are inserted between carbon-carbon bonds of a hydrocarbon group having 2 to 20 carbon atoms; (2) a group in which 1 to 5 hydrogen atoms bonded to a carbon atom of a hydrocarbon group having 1 to 12 carbon atoms or the group of (1) are substituted with one or more polar groups selected from the group consisting of a hydroxy group, a mercapto group, -NH C(O)NH ２ group, and -C(O)NH ２ group. In the formula A ２２ , B ２２ is a monovalent or divalent group that does not contain a hydrophobic group having 8 or more carbon atoms, and is (3) a hydrogen atom; (4) a hydrocarbon group having 1 to 7 carbon atoms; (5) a group in which one or more bonds selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, and an ester bond are inserted between carbon-carbon bonds of a hydrocarbon group having 2 to 20 carbon atoms; (6) a group in which 1 to 5 hydrogen atoms bonded to a carbon atom of a hydrocarbon group having 1 to 12 carbon atoms or the group of (5) are substituted with one or more polar groups selected from the group consisting of a hydroxy group, a mercapto group, -NH C(O)NH ２ group, and -C(O)NH ２ group. R ２２ is, when B ２２ is a monovalent group, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and when B ２２ is a divalent group, it is a single bond that connects N and B ２２ in the formula. In the formula A ２３ , B ２３The group is a monovalent or divalent group that does not contain a hydrophobic group with 8 or more carbon atoms, and (7) a hydrocarbon group having 1 to 7 carbon atoms, (8) a hydrocarbon group having 2 to 20 carbon atoms in which one or more bonds selected from the group consisting of ether bonds, amide bonds, urea bonds, urethane bonds, sulfide bonds, and ester bonds are inserted between the carbon-carbon bonds, and (9) one to five hydrogen atoms bonded to the carbon atoms of the group in (7) or (8) are a hydroxyl group, a mercapto group, or -NHC(O)NH ２ Base, and -C(O)NH ２ (10) A group substituted with one or more polar groups selected from the group consisting of groups, or a hydrogen atom, R ２３ B ２３ If it is a monovalent group, it is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, B ２３ If it is a divalent group, then N and B in the formula ２３ It is a single bond that connects and.

[25] An oil-repellent composition according to any one of [1] to

[24] for pulp or paper applications.

[26] An oil-repellent composition according to [2], further comprising a non-aqueous medium to impart oil repellency to a porous body.

[27] An article in which at least a portion of the base material is treated with an oil-repellent composition according to any one of [1] to

[25] .

[28] An article according to

[27] , wherein the base material is pulp or paper.

[0006] [A1] An oil-repellent composition comprising a copolymer containing a unit based on a monomer represented by the following formula 1, and a unit based on a nonionic monomer having a solubility in water of 1 g / 100 mL or more at 20°C. １ -A １ -B １ ... (Equation 1) In Equation 1 above, X １ A is a monovalent polymerizable reactive group, １ is a divalent organic group, B １ X is a monovalent organic group having at least one trialkylsilyl group. [A2] The above X １ is a (meth)acryloyloxy group, and the B １ The oil-repellent composition according to [A1], wherein is a monovalent organic group represented by formula 3 below or a monovalent organic group represented by formula 4 below. n is an integer between 0 and 3. Ａ１ *- is A １ [A3] The oleophobic composition according to [A1] or [A2], wherein the copolymer further comprises units based on an ionic monomer. [A4] The oleophobic composition according to [A3], wherein the content of the units based on the ionic monomer is greater than 0% by mass and less than 29% by mass with respect to the total number of units constituting the copolymer. [A5] The oleophobic composition according to [A3] or [A4], wherein the ionic monomer is a monomer having an ion donating group. [A6] The oleophobic composition according to [A5], further comprising a base or an acid, wherein some or all of the ion donating groups are ionized by the base or acid. [A7] The oleophobic composition according to [A6], wherein the acid is an organic acid. [A8] The oleophobic composition according to [A7], wherein the organic acid is at least one selected from the group consisting of acetic acid, lactic acid, and malic acid. [A9] The oil-repellent composition according to any one of [A1] to [A8], wherein the content of units based on the monomer represented by formula 1 is 10% by mass or more and 55% by mass or less with respect to the total units constituting the copolymer. [A10] An oil-repellent composition comprising a copolymer containing units based on a monomer represented by the following formula 1, units based on a nonionic monomer represented by the following formula 2, and units based on an ionic monomer having an ion-donating group or an ionic moiety and not containing a hydrophobic group having 8 or more carbon atoms, wherein the content of the units based on the ionic monomer is greater than 0% by mass and less than 29% by mass with respect to the total units constituting the copolymer. X １ -A １ -B １ ... (Equation 1) In Equation 1 above, X １ is a (meth)acryloyloxy group, A １ is a divalent organic group, B １ This is a monovalent organic group represented by formula 3 below or a monovalent organic group represented by formula 4 below. n is an integer between 0 and 3. Ａ１ *- is A １ This is a combination with CH. ２ = C(R ２１ ) - A ２ ... (Equation 2) In Equation 2 above, R ２１is a hydrogen atom, a halogen atom, or a methyl group, A ２ The following equation A ２１ A ２２ Or A ２３ This is the group represented by -C(O)-O-B ２１ ...(Formula A ２１ ) -C(O)-N(R ２２ )-B ２２ ...(Formula A ２２ ) -N(R ２３ )-C(O)-B ２３ ...(Formula A ２３ ) Equation A ２１ Medium, B ２１ This is a monovalent group that does not contain a hydrophobic group with 8 or more carbon atoms, and (1) a group in which one or more bonds selected from the group consisting of ether bonds, amide bonds, urea bonds, urethane bonds, sulfide bonds, and ester bonds are inserted between the carbon-carbon bonds of a hydrocarbon group having 2 to 20 carbon atoms, or (2) one to five hydrogen atoms bonded to the carbon atoms of a hydrocarbon group having 1 to 12 carbon atoms or the group in (1) are hydroxyl groups, mercapto groups, -NHC(O)NH ２ Base, and -C(O)NH ２ It is one of the following: a group substituted with one or more polar groups selected from the group consisting of groups. ２２ Medium, B ２２ The group is a monovalent or divalent group that does not contain a hydrophobic group with 8 or more carbon atoms, and (3) a hydrogen atom, (4) a hydrocarbon group having 1 to 7 carbon atoms, (5) a hydrocarbon group having 2 to 20 carbon atoms in which one or more bonds selected from the group consisting of ether bonds, amide bonds, urea bonds, urethane bonds, sulfide bonds, and ester bonds are inserted between the carbon-carbon bonds, or (6) a hydrocarbon group having 1 to 12 carbon atoms or 1 to 5 hydrogen atoms bonded to the carbon atoms of the group in (5) are a hydroxyl group, a mercapto group, or -NHC(O)NH ２ Base, and -C(O)NH ２ R is one of the groups that are substituted with one or more polar groups selected from the group consisting of groups, ２２ B ２２ If it is a monovalent group, it is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, B ２２ If it is a divalent group, then N and B in the formula２２ It is a single bond connecting and . Equation A ２３ Medium, B ２３ (7) A hydrocarbon group having 1 to 7 carbon atoms, (8) A hydrocarbon group having 2 to 20 carbon atoms, in which one or more bonds selected from the group consisting of ether bonds, amide bonds, urea bonds, urethane bonds, sulfide bonds, and ester bonds are inserted between the carbon-carbon bonds, (9) One to five hydrogen atoms bonded to the carbon atoms of the group in (7) or (8) are hydroxyl groups, mercapto groups, -NHC(O)NH ２ Base, and -C(O)NH ２ R is one of the groups that are substituted with one or more polar groups selected from the group consisting of groups, ２３ B ２３ If it is a monovalent organic group, it is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and B ２３ If it is a divalent organic group, then N and B in the formula ２３ It is a single bond that connects and . A method for producing the oil-repellent composition described in [A11] and [A6], comprising polymerizing the monomer represented by formula 1, the nonionic monomer, and the ionic monomer, and then mixing the acid or base to ionize some or all of the ion donor groups. [A12] An article in which the substrate is treated with the oil-repellent composition described in any of [A1] to [A10]. [A13] An article in which the substrate is paper or fiber described in [A12]. [A14] Oil-resistant paper in which the pulp or paper is treated with the oil-repellent composition described in any of [A1] to [A10].

[0007] [B1] An oil-repellent composition comprising a copolymer containing a unit based on a monomer represented by the following formula 1, a unit based on a monomer having a cation-donating group, and a unit based on a monomer having an anion-donating group. １ -A １ -B １ ... (Equation 1) In Equation 1 above, X １ A is a monovalent polymerizable reactive group, １ is a divalent organic group, B １ is a monovalent organic group having at least one trialkylsilyl group. [B2] The above B１ The oil-repellent composition according to [B1], wherein the monovalent organic group is represented by formula 3 below or by formula 4 below. Ａ１＊ -Si(OSiR) １５ ３ ) ３－ｂ R １６ ｂ ...(Formula 3) Ａ１＊ -SiR １７ ２ (OSiR １８ ２ ) ｎ OSiR １９ ３ ... (Equation 4) In Equation 3 above, R １５ These are each independently of -OSiR １５１ ３ , or a linear or branched alkyl group having 1 to 6 carbon atoms, R １５１ Each of these is independently a linear or branched alkyl group having 1 to 6 carbon atoms, and R １６ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms, and b is an integer from 0 to 2. Ａ１＊ - is A １ This is a coupling with. In the above formula 4, R １７ , R １８ and R １９ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms, and n is an integer from 0 to 10. Ａ１＊ - is A １ This is a joint with [B3] the above B １ The oil-repellent composition according to [B1], wherein the monovalent organic group is represented by the following formula 31 or the monovalent organic group is represented by the following formula 41. In formulas 31 and 41, Ａ１ *- is A １The bonding is between and n, where n is an integer from 0 to 3. [B4] The oleophobic composition according to any one of [B1] to [B3], wherein the cation donor group is one or more selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and a pyridyl group. [B5] The oleophobic composition according to any one of [B1] to [B4], wherein the anion donor group is one or more selected from the group consisting of a carboxyl group, a sulfo group, a phenolic hydroxyl group, and a phosphoric acid group. [B6] The oleophobic composition according to any one of [B1] to [B5], further comprising at least one of a base and an acid, wherein at least a portion of the cation donor group and the anion donor group are ionized by the base or acid, respectively. [B7] The oleophobic composition according to [B6], wherein the base is one or more selected from alkali metal hydroxides, amines, and ammonia. [B8] The oleophobic composition according to [B6], wherein the acid is a polycarboxylic acid. [B9] The oil-repellent composition according to any one of [B1] to [B8], further comprising units based on a nonionic monomer. [B10] The oil-repellent composition according to any one of [B1] to [B9], wherein the total content of units based on a monomer having a cation donor group and units based on a monomer having an anion donor group is greater than 0% by mass and less than 29.0% by mass relative to all units constituting the copolymer. [B11] The oil-repellent composition according to any one of [B1] to [B10], wherein the content of units based on monomer 1 represented by formula 1 is 10.0% by mass or more and 55.0% by mass or less relative to all units constituting the copolymer. [B12] The oil-repellent composition according to any one of [B1] to [B11] for paper applications. A method for producing an oil-repellent composition according to any one of [B1] to [B12], comprising polymerizing a monomer represented by formula 1, a monomer having a cation donor group, and a monomer having an anion donor group, and then mixing at least one of the base and the acid to ionize at least a portion of the cation donor group and the anion donor group. [B14] An article in which at least a portion of the substrate is treated with an oil-repellent composition according to any one of [B1] to [B12]. [B15] The article according to [B14], wherein the substrate is pulp or paper.

[0008] According to this disclosure, it is possible to provide an oil-repellent composition, an article, and a method for producing an oil-repellent composition that yields an article with excellent oil-repellent properties.

[0009] The meanings and definitions of terms used in this disclosure are as follows: "Monomer-based unit" refers to 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(oxy) group" is a general term for acryloyl group, acryloyloxy group, methacryloyl group, and methacryloyloxy group, and (meth)acrylic acid is a general term for acrylic acid and methacrylic acid. The same interpretations shall apply to (meth)acrylamide and others. Solubility in water is the value at 20°C. Solubility in water is measured in accordance with JIS K 8001. The number-average molecular weight (hereinafter also referred to as "Mn") and weight-average molecular weight (hereinafter also referred to as "Mw") of the 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 the 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 the 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.

[0010] ≪Oil-Repellent Composition≫ An oil-repellent composition according to one embodiment of the present disclosure comprises at least one selected from copolymer A and copolymer B. Hereinafter, copolymer A and copolymer B will be collectively referred to simply as "polymer". The oil-repellent composition may contain a liquid medium. The oil-repellent composition may contain other components as needed. The oil-repellent composition may be the solution or dispersion itself obtained by the copolymer manufacturing method described later, or it may be a solution, dispersion, or a diluted solution thereof to which other components have been added.

[0011] <Copolymer A> Copolymer A contains units based on a monomer represented by formula 1 (hereinafter also referred to as "monomer 1") (hereinafter also referred to as "unit 1") and units based on a nonionic monomer (hereinafter also referred to as "monomer 2") having a solubility in water of 1 g / 100 mL or more at 20°C (hereinafter also referred to as "unit 2"). Units that fall under both unit 1 and unit 2 are treated as unit 1. Unit 1 and unit 2 in copolymer A may each consist of one type or two or more types. Copolymer A may further contain units based on an ionic monomer (hereinafter also referred to as "monomer 3") (hereinafter also referred to as "unit 3"). Unit 3 in copolymer A may consist of one type or two or more types. Copolymer A may further contain units based on other monomers other than monomer 1, monomer 2, and monomer 3 (hereinafter also referred to as "monomer 4") (hereinafter also referred to as "unit 4"). The unit 4 in copolymer A may be one type or two or more types.

[0012] (Unit 1) Unit 1 is a unit based on monomer 1, and monomer 1 is a monomer represented by the following equation 1. １ -A １ -B １ ... (Equation 1) In Equation 1 above, 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.

[0013] [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 5 below, and monovalent groups represented by formula 6 below, with monovalent groups represented by formula 6 below being preferred.

[0014] In the above formula 5, 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, or a C1-C4 alkyl group which may be halogenated. １０１ ~R １０５ Of these, A １ The connection with is R １０３ ~R １０５ It is preferable that R １０４ It is more preferable that this is the case. 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 The bonds that are not linked to the other are preferably, independently, a hydrogen atom or a monovalent hydrocarbon group which may be halogenated, with a hydrogen atom being more preferred. As for halogens, those other than fluorine are preferred, with chlorine being more preferred.

[0015] * Ａ１ -R １１ C(=O)CR １３ =CH ２ ... (Equation 6) In Equation 6 above, 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, 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.

[0016] R １１ is an oxygen atom or NR １２ A divalent group represented by is preferred, and an oxygen atom is more preferred. １２ The monovalent organic group in this is a linear or branched alkyl group having 1 to 12 carbon atoms, 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 R. １２ R is preferably a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. １３ R is preferably a hydrogen atom, a chlorine atom, or a linear alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group. １１ is an oxygen atom, and R １３ When R is a hydrogen atom or a methyl group, formula 6 represents a (meth)acryloyloxy group. １１ NR １２ It is a divalent group represented by and R １３ When is a hydrogen atom or a methyl group, formula 6 represents a (meth)acrylamide group.

[0017] The monovalent group represented by the above formula 6 is preferably a (meth)acryloyloxy group or a (meth)acrylamide group, and more preferably a (meth)acryloyloxy group.

[0018] Examples of hydrolyzable silyl groups include the monovalent group represented by formula 7 below.

[0019] * Ａ１ -SiR １４ ３－ａ X ａ ... (Equation 7) In Equation 7 above, R １４ X is a monovalent organic group having 1 to 20 carbon atoms, excluding hydrolyzable groups, where X represents a hydroxyl group, a halogen atom, 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.

[0020] R １４ The hydrolyzable groups in "organic groups other than hydrolyzable groups" are exemplified by those similar to the hydrolyzable groups of X described later. １４ The 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 members 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.

[0021] Examples of hydrolyzable groups of X include alkoxy groups, acyloxy groups, ketoxymate 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. The alkoxy group is preferably a methoxy group, ethoxy group, or isopropoxy group, with methoxy or ethoxy groups being more preferred. When the alkoxy group is a methoxy or ethoxy group, siloxane bonds are readily formed.

[0022] Examples of hydrolyzable silyl groups represented by the above formula 7 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.

[0023] [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 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 containing the above-mentioned divalent groups having heteroatoms. A １ It does not contain silicon atoms.

[0024] The number of carbon atoms in the divalent organic group is preferably 1 to 20, more preferably 2 to 20, even more preferably 2 to 16, particularly preferably 2 to 10, and most preferably 2 to 6. When the number of carbon atoms is below the above upper limit, the oil-repellent and water-repellent properties are even better.

[0025] A １ The divalent organic group is preferably 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, or octylene group, or 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, or propyl group, and more preferably a linear alkylene group. Among the linear alkylene groups, a linear alkylene group having 2 to 6 carbon atoms is preferred.

[0026] A １Specific examples include: Ｘ１＊ - [CH ２ C(O)NH] ｎ１ (CH ２ ) ３ - ＊Ｂ１ , 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, preferably between 0 and 2. Ｘ１＊ - is X １ This is a combination of - ＊Ｂ１ is B １ This is a combination of the two.

[0027] [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, even more preferably 1 to 3, particularly preferably 2 to 3, and most preferably 3. When the number of trialkylsilyl groups is within the above range, the effect of imparting oil repellency to the treated article is superior. B １ If the compound has two or more trialkylsilyl groups, the multiple trialkylsilyl groups may be the same or different.

[0028] Examples of alkyl groups in the trialkylsilyl group include linear or branched alkyl groups having 1 to 6 carbon atoms, with t-butyl, isopropyl, ethyl, and methyl groups being preferred, ethyl and methyl groups being more preferred, and methyl groups being particularly preferred. The three alkyl groups of the trialkylsilyl group may be the same or different.

[0029] B １ It is preferable that it has a siloxane bond. １The number of Si-O bonds 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 effect of imparting oil repellency to the treated article is superior. B １ The silicon number is preferably 20 or less, more preferably 10 or less, even more preferably 1 to 8, even more preferably 1 to 6, particularly preferably 2 to 5, and most preferably 3 to 4.

[0030] A １ B combines with １ The atom inside is preferably a silicon atom. B １ Preferably, the monovalent organic group is represented by formula 3 below or by formula 4 below, and more preferably by formula 3 below.

[0031] Ａ１＊ -Si(OSiR) １５ ３ ) ３－ｂ R １６ ｂ ... (Equation 3) In Equation 3 above, R 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, R 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 independently a linear or branched alkyl group having 1 to 6 carbon atoms, and R １６ Each of these is independently a linear or branched alkyl group having 1 to 6 carbon atoms, b is an integer from 0 to 2, and c is an integer from 0 to 2. Ａ１＊ - is A １ This is a combination of the two.

[0032] Ａ１＊ -SiR １７ ２ (OSiR​​１８ ２ ) ｎ OSiR １９ ３ ... (Equation 4) In Equation 4 above, R １７ , R １８ and R １９ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms, and n is an integer from 0 to 10. Ａ１＊ - is A １ This is a combination of the two.

[0033] In formula 3, b is an integer between 0 and 2, preferably 0 or 1. In formula 3, R 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, with a linear or branched alkyl group having 1 to 6 carbon atoms being preferred. １５１ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms. １５２ R is a single-bonded or linear or branched alkylene group having 1 to 6 carbon atoms, with single bonds being preferred. １５３ Each is independently a linear or branched alkyl group having 1 to 6 carbon atoms. c is an integer from 0 to 2, preferably an integer from 0 to 1, and more preferably 0. In formula 3, R １６ Each of these is independently a linear or branched alkyl group having 1 to 6 carbon atoms, with linear alkyl groups having 1 to 6 carbon atoms being preferred, and methyl groups being more preferred. １５ , R １５１ , R １５３ and R １６ The linear or branched alkyl group in is preferably a methyl group, ethyl group, isopropyl group, or t-butyl group, more preferably a methyl group or ethyl group, and even more preferably a methyl group. １５２ In formula 3, the linear or branched alkylene group is preferably a methylene group or an ethylene group, and more preferably an ethylene group. １５These 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.

[0034] The group represented by formula 3 above is preferably the group represented by formula 31 or 32 below, and more preferably the group represented by formula 31 below. In formula 31 or 32, Ａ１ *- is A １ This is a combination of the two.

[0035]

[0036] In Equation 4, n is an integer from 0 to 6, preferably an integer from 0 to 3. In Equation 4, R １７ , R １８ and R １９ Each of these is independently a linear or branched alkyl group having 1 to 6 carbon atoms. Preferred linear or branched alkyl groups are methyl, ethyl, isopropyl, and t-butyl groups, more preferably methyl and ethyl groups, and even more preferably methyl groups. In particular, R １９ It is preferable that R is an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. In formula 4, multiple R １７ These may be the same or different, and there may be multiple R １９ These may be the same or different. If n is 1 or greater, there may be multiple R １８ These may be the same or different.

[0037] As the base represented by the above formula 4, the base represented by the following formula 41 is preferred. In formula 41, Ａ１ *- is A １ This is a combination of the two.

[0038] In equation 41, n is the same as n in equation 4.

[0039] The molecular weight of monomer 1 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 1 is preferably 200 or more and less than 1,000, more preferably 200 or more and less than 500, and even more preferably 300 or more and 450 or less, from the viewpoint of oil repellency. In particular, B in monomer 1 １ When is a group represented by formula 3, the molecular weight of monomer 1 is preferably 200 or more and less than 1,000, more preferably 200 or more and less than 500, and even more preferably 300 or more and 450 or less. B in monomer 1 １ When is a group represented by formula 4, the molecular weight of monomer 1 is preferably 200 or more and less than 500.

[0040] Examples of monomer 1 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, N-(tris(trimethylsiloxy)silylpropyl)(meth)acrylamide, etc., with 3-((meth)acryloyloxy)propyltris(trimethylsiloxy)silane, 3-((meth)acryloyloxy)propylbis(trimethylsiloxy)methylsilane, and N-(tris(trimethylsiloxy)silylpropyl)(meth)acrylamide being preferred, and 3-((meth)acryloyloxy)propyltris(trimethylsiloxy)silane being more preferred.

[0041] (Unit 2) Unit 2 is a unit based on monomer 2, which is a nonionic monomer having a solubility in water of 1 g / 100 mL or more. Nonionic means that it does not have an ion-donating group or ionic site, as described later. By combining Unit 1 and Unit 2, copolymer A becomes less likely to swell with oil droplets or less likely to dissolve in oil droplets, thus improving the oil repellency of the resulting article. The solubility of monomer 2 in water is preferably 2 g / 100 mL or more, and more preferably 5 g / 100 mL or more. The higher the solubility of monomer 2 in water, the better, and there is no particular upper limit, but for example, it is preferable that it is miscible with water. Miscible with water means that it dissolves in water at any concentration.

[0042] Monomer 2 preferably has a polymerizable reactive group. Examples of polymerizable reactive groups include groups having a polymerizable carbon-carbon double bond and hydrolyzable groups, with groups having a polymerizable carbon-carbon double bond being preferred. Examples of groups having a polymerizable carbon-carbon double bond and hydrolyzable 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.

[0043] X １ If the group has a polymerizable carbon-carbon double bond, it is preferable that the polymerizable reactive group of monomer 2 also has a polymerizable carbon-carbon double bond. １ The polymerizable carbon-carbon double bond groups of monomer 2 may be the same or different, but it is preferable that they be the same.

[0044] X １ If the group is hydrolyzable, then the polymerizable reactive group of monomer 2 is also preferably hydrolyzable. １ The hydrolyzable groups of monomer 2 may be the same or different, but they are preferably the same.

[0045] From the viewpoint of solubility in water, monomer 2 preferably has a heteroatom and a hydrogen atom bonded to the heteroatom. The heteroatom is an atom other than carbon and hydrogen atoms, and examples include nitrogen, oxygen, sulfur, boron, phosphorus, and silicon atoms, with nitrogen and oxygen atoms being preferred. It may also have two or more types of heteroatoms.

[0046] Monomer 2 preferably has polar groups from the viewpoint of solubility in water. Examples of polar groups include amide groups, urethane groups, urea groups, hydroxyl groups, mercapto groups, and ether groups. It may have two or more types of polar groups. The number of polar groups is not particularly limited, but two or more is preferable because it makes it easier to obtain copolymer A with high oil repellency without using ionic monomer 3. Monomer 2 preferably contains at least one selected from the group consisting of amide groups, urethane groups, urea groups, hydroxyl groups, and mercapto groups, more preferably at least one selected from the group consisting of amide groups, urethane groups, and hydroxyl groups, and even more preferably a hydroxyl group. It may further contain other polar groups.

[0047] It is preferable that monomer 2 satisfies one or both of the following requirements 1 and 2. Satisfying one or both of requirements 1 and 2 tends to result in better oil repellency. Requirement 1: The value obtained by dividing the molecular weight of monomer 2 by the number of heteroatom-hydrogen atom bonds in monomer 2 (molecular weight / number of heteroatom-hydrogen atom bonds) is 150 or less. From the viewpoint of improving oil repellency, the molecular weight / number of heteroatom-hydrogen atom bonds is preferably 140 or less, and more preferably 130 or less. Also, values ​​of 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, and 90 or more are preferred. The above upper and lower limits can be combined as appropriate. For example, from the viewpoint of improving oil repellency, the molecular weight / number of heteroatom-hydrogen atom bonds is preferably 30 to 150, 50 to 150, 80 to 150, 90 to 150, and 90 to 140. Requirement 2: The value obtained by dividing the molecular weight of monomer 2 by the number of polar groups in monomer 2 (molecular weight / number of polar groups) is 150 or less. From the viewpoint of improving oil repellency, the molecular weight / number of polar groups is preferably 140 or less, and more preferably 130 or less. Also, values ​​of 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, and 90 or more are preferred. The above upper and lower limits can be combined as appropriate. For example, from the viewpoint of improving oil repellency, the molecular weight / number of polar groups is preferably 30 to 150, 50 to 150, 80 to 150, 90 to 150, and 90 to 140.

[0048] From the viewpoint of improving oil repellency, the molecular weight of monomer 2 is preferably 60 to 1,500, 60 to 450, 60 to 200, 70 to 180, 70 to 170, 70 to 160, 80 to 160, 90 to 160, or 90 to 150.

[0049] Monomer 2 may have a polyoxyalkylene chain, but it is also preferable that it does not have a polyoxyalkylene chain from the viewpoint of imparting oil repellency to the treated article. The polyoxyalkylene chain is (LO) ｍIt is represented as follows: LO is an oxyalkylene group, and m is an integer of 2 or more. The m LOs may be the same or different. The number of carbon atoms in the oxyalkylene group represented by LO is preferably 2 to 6, more preferably 2 to 4. The oxyalkylene group is preferably an oxyethylene group, an oxypropylene group, an oxybutylene group, or an oxytetramethylene group, with the oxyethylene group being particularly preferred. m is preferably 2 to 100, more preferably 2 to 8, and particularly preferably 2 to 4. A smaller m is preferable. It is preferable that monomer 2 does not have a polyoxyalkylene chain where m is preferably 9 or more, more preferably 5 or more, and even more preferably 3 or more.

[0050] A preferred example of monomer 2 is the monomer represented by the following formula 2: CH ２ = C(R ２１ ) - A ２ ... (Equation 2) In Equation 2 above, R ２１ is a hydrogen atom, a halogen atom, or a methyl group, A ２ The following equation A ２１ A ２２ Or A ２３ This is the group represented by -C(O)-O-B ２１ ...(Formula A ２１ ) -C(O)-N(R ２２ )-B ２２ ...(Formula A ２２ ) -N(R ２３ )-C(O)-B ２３ ...(Formula A ２３ ) Equation A above ２１ Medium, B ２１ A monovalent group is (1) a hydrocarbon group having 2 to 20 carbon atoms in which one or more bonds selected from the group consisting of ether bonds, amide bonds, urea bonds, urethane bonds, sulfide bonds, and ester bonds are inserted between the carbon-carbon bonds, or (2) a hydrocarbon group having 1 to 12 carbon atoms or 1 to 5 hydrogen atoms bonded to the carbon atoms of the group in (1) above, which are a hydroxyl group, a mercapto group, or -NHC(O)NH ２ Base, and -C(O)NH ２ It is one of the following: a group substituted with one or more polar groups selected from the group consisting of groups.２２ Medium, B ２２ The group is monovalent or divalent, and (3) a hydrogen atom, (4) a hydrocarbon group having 1 to 7 carbon atoms, (5) a hydrocarbon group having 2 to 20 carbon atoms in which one or more bonds selected from the group consisting of ether bonds, amide bonds, urea bonds, urethane bonds, sulfide bonds, and ester bonds are inserted between the carbon-carbon bonds, or (6) a hydrocarbon group having 1 to 12 carbon atoms or 1 to 5 hydrogen atoms bonded to the carbon atoms of the group in (5) above, which are hydroxyl groups, mercapto groups, -NHC(O)NH ２ Base, and -C(O)NH ２ R is one of the groups that are substituted with one or more polar groups selected from the group consisting of groups, ２２ B ２２ If it is a monovalent group, it is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, B ２２ If it is a divalent group, then N and B in the formula ２２ It is a single bond connecting and . Equation A above ２３ Medium, B ２３ The group is monovalent or divalent, and (7) a hydrocarbon group having 1 to 7 carbon atoms, (8) a hydrocarbon group having 2 to 20 carbon atoms in which one or more bonds selected from the group consisting of ether bonds, amide bonds, urea bonds, urethane bonds, sulfide bonds, and ester bonds are inserted between the carbon-carbon bonds, and (9) one to five hydrogen atoms bonded to the carbon atoms of the group in (7) or (8) above are a hydroxyl group, a mercapto group, or -NHC(O)NH ２ Base, and -C(O)NH ２ (10) A group substituted with one or more polar groups selected from the group consisting of groups, and R ２３ B ２３ If it is a monovalent group, it is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, B ２３ If it is a divalent group, then N and B in the formula ２３It is a single bond connecting (1), (2), (4), (5), (7), and (8) above. The hydrocarbon groups in each of the above groups may be linear, cyclic, or a combination thereof, and may be saturated or unsaturated. The linear hydrocarbon groups may be linear or branched. Examples of monovalent hydrocarbon groups include alkyl groups, alkenyl groups, aryl groups, and aralkyl groups. Examples of divalent hydrocarbon groups include alkylene groups and arylene groups. In each of the above groups (1), (5), and (8), the number of carbon atoms in the carbon chain not interrupted by the above bond is preferably 10 or less, more preferably 7 or less, and even more preferably 4 or less.

[0051] From the viewpoint of solubility in water, monomer 2 preferably does not contain hydrophobic groups having 8 or more carbon atoms. Examples of hydrophobic groups include hydrocarbon groups. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, aryl groups, and aralkyl groups. If monomer 2 contains hydrocarbon groups, the number of carbon atoms is preferably 7 or less, more preferably 6 or less, and even more preferably 5 or less.

[0052] Examples of monomer 2 include the following compounds.

[0053] However, R is either a hydrogen atom or a methyl group.

[0054] Examples of monomer 2 include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, N-vinylformamide, 2-methoxyethyl (meth)acrylate, 2-(acetylamino)ethyl (meth)acrylate, 2-ureidoethyl (meth)acrylate, (meth)acrylamide, N-methyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-(2-hydroxyethyl) (meth)acrylamide, N-(methoxymethyl) (meth)acrylamide, N-(hydroxymethyl) (meth)acrylamide, N-(2-hydroxypropyl) (meth)acrylamide, N-vinylacetamide, N-vinylpyrrolidone, etc., with 2-hydroxyethyl (meth)acrylate, N-vinylformamide, and N-vinylacetamide being more preferred, and 2-hydroxyethyl (meth)acrylate being particularly preferred.

[0055] (Unit 3) Unit 3 is a unit based on monomer 3, which is an ionic monomer. Ionic monomers have ion-donating groups or ionic moieties. In other words, unit 3 has ion-donating groups or ionic moieties. Note that "monomer 3 has ionic moieties" means that one molecule of monomer 3 can form ions within the molecule. Ion-donating groups will be explained in detail later. By further combining unit 3 with units 1 and 2, the oil repellency of articles treated with an oil-repellent composition containing copolymer A is further improved.

[0056] Monomer 3 preferably has a polymerizable reactive group. Examples of polymerizable reactive groups include groups having a polymerizable carbon-carbon double bond and hydrolyzable groups, with groups having a polymerizable carbon-carbon double bond being preferred. Examples of groups having a polymerizable carbon-carbon double bond and hydrolyzable 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.

[0057] X １If the group has a polymerizable carbon-carbon double bond, it is preferable that the polymerizable reactive group of monomer 3 also has a polymerizable carbon-carbon double bond. １ The polymerizable carbon-carbon double bond groups of monomer 3 may be the same or different, but it is preferable that they be the same.

[0058] X １ If the group is hydrolyzable, then the polymerizable reactive group of monomer 3 is also preferably a hydrolyzable group. １ The hydrolyzable groups of monomer 3 may be the same or different, but they are preferably the same.

[0059] From the viewpoint of oil repellency, monomer 3 is preferably free of hydrophobic groups having 8 or more carbon atoms, and more preferably free of hydrophobic groups having 6 or more carbon atoms. Examples of hydrophobic groups include hydrocarbon groups. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, aryl groups, and aralkyl groups.

[0060] Monomer 3 preferably has an ion-donating group from the viewpoint of oil repellency and manufacturing stability. An ion-donating group is a group that is ionized by a base or an acid. Examples of ion-donating groups include anion-donating groups that are ionized by a base and cation-donating groups that are ionized by an acid. Some or all of the ion-donating group may be ionized to form a salt, and it is preferable that some or all of it be ionized to form a salt.

[0061] Examples of monomer 3 include monomers having an anion-donating group (hereinafter referred to as "monomer 31"), monomers having a cation-donating group (hereinafter referred to as "monomer 32"), and monomers having ionic moieties other than monomers 31 and 32 (hereinafter referred to as "monomer 33"), with monomers 31 and 32 being more preferred. Monomers 31, 32, and 33 may be used individually or in combination. However, if copolymer A contains monomer 31 or monomer 32, it is preferable that it contains only one of them. In other words, if copolymer A contains units based on monomer 31, it is preferable that copolymer A does not contain units based on monomer 32. Also, if copolymer A contains units based on monomer 32, it is preferable that copolymer A does not contain units based on monomer 31.

[0062] (Unit 31) Unit 31 is a unit based on monomer 31, which is a monomer having an anion donor group.

[0063] The monomer 31 preferably has a polymerizable reactive group. Examples of polymerizable reactive groups are the same as those described for monomer 3, and the preferred embodiments are the same as those for monomer 3.

[0064] From the viewpoint of oil repellency, monomer 31 is preferably free of hydrophobic groups having 8 or more carbon atoms, and more preferably free of hydrophobic groups having 6 or more carbon atoms. Examples of hydrophobic groups include hydrocarbon groups. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, aryl groups, and aralkyl groups.

[0065] An anion donor group is a group that is ionized by a base. Some or all of the anion donor group may be ionized to form a salt, and it is preferable that some or all of it be ionized to form a salt.

[0066] Examples of anion donor groups include carboxyl groups, sulfol groups, phenolic hydroxyl groups, and phosphate groups. Among these, carboxyl groups are preferred. Examples of salts of anion donor groups include alkali metal salts (such as sodium salts), alkaline earth metal salts, and ammonium salts (such as methylammonium salt, ethanolammonium salt, and triethanolammonium salt), with alkali metal salts being preferred and sodium salts being more preferred.

[0067] The anion-donating group may form two or more salts.

[0068] Preferred monomers 31 include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, vinylbenzenesulfonic acid, acrylamide tert-butylsulfonic acid, 6-acrylamidohexanoic acid, and others, with (meth)acrylic acid being more preferred.

[0069] Examples of cases where monomer 31 forms a salt include the following compounds.

[0070] However, R is a hydrogen atom or a methyl group, and B ＋ This is a countercation (derived from a base). The counteranion and countercation can be monovalent or polyvalent. Multiple B ＋ They may be the same or different.

[0071] (Unit 32) Unit 32 is a unit based on monomer 32, which is a monomer having a cation donor group (hereinafter sometimes referred to as a "cationic monomer").

[0072] The monomer 32 preferably has a polymerizable reactive group. Examples of polymerizable reactive groups are the same as those described for monomer 3, and the preferred embodiments are the same as those for monomer 3.

[0073] X １ If the group has a polymerizable carbon-carbon double bond, it is preferable that the polymerizable reactive group of monomer 32 also has a polymerizable carbon-carbon double bond. １The polymerizable carbon-carbon double bond-containing groups of monomer 32 may be the same or different, respectively, and the same is preferred.

[0074] X １ When X is a hydrolyzable group, the polymerizable reactive group of monomer 32 is also preferably a hydrolyzable group. X １ The hydrolyzable groups of X and monomer 32 may be the same or different, respectively, and the same is preferred.

[0075] From the viewpoint of oil repellency, monomer 32 preferably does not contain a hydrophobic group having 8 or more carbon atoms, and more preferably does not contain a hydrophobic group having 6 or more carbon atoms. Examples of the hydrophobic group include hydrocarbon groups. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, and an aralkyl group.

[0076] The cation-donating group is a group that ionizes by an acid. The cation-donating group may be partially or entirely ionized to form a salt, and it is preferred that a part or all of it is ionized to form a salt.

[0077] Examples of the cation-donating group include a primary amino group, a secondary amino group, a tertiary amino group, and a pyridyl group. Among these, a tertiary amino group and a pyridyl group are preferred, and a tertiary amino group is more preferred. The cation-donating group preferably has a heterocyclic ring from the viewpoint of excellent oil repellency imparting effect to the treated article in combination with polyvinyl alcohol described later. Examples of the cation-donating group having a heterocyclic ring include a pyridyl group. Examples of the salt of the cation-donating group include an inorganic acid salt or an organic acid salt, and an organic acid salt is preferred.

[0078] Examples of the inorganic acid for obtaining the inorganic acid salt include hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and the like.

[0079] Examples of the organic acid for obtaining the organic acid salt include carboxylic acids. The carboxylic acid may be a natural product, a synthetic product, or a semi-synthetic product. As the carboxylic acid, a monovalent or polyvalent carboxylic acid is preferred.

[0080] Examples of monobasic carboxylic acids include formic acid, acetic acid, propionic acid, lactic acid, etc. Examples of polybasic carboxylic acids include aliphatic polybasic carboxylic acids (oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, etc.), hydroxy polybasic carboxylic acids having a hydroxy group in the molecule (tartaric acid, malic acid, citric acid, tartronic acid, etc.), aromatic polybasic carboxylic acids (phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, etc.), and polymeric polybasic carboxylic acids (poly(meth)acrylic acid, alginic acid, polycarboxylic acid, hyaluronic acid, etc.).

[0081] As the carboxylate, a salt with a monobasic carboxylic acid or a salt with a hydroxy polybasic carboxylic acid is preferable, and from the viewpoints of safety, water dispersibility, and safety of the chlorinated copolymer, acetate, lactate, malate, citrate, or itaconate is more preferable, acetate, lactate, and malate are particularly preferable, and acetate is most preferable.

[0082] The cation-donating group may form two or more kinds of salts.

[0083] Examples of the monomer 32 include aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, aminoethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, allylamine, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, etc. Aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc. are more preferable, and diethylaminoethyl (meth)acrylate is most preferable. Also, from the viewpoint of combination with polyvinyl alcohol described later, a monomer 32 having a heterocyclic ring is preferable, and for example, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, etc. are preferable.

[0084] Examples of the case where the monomer 32 forms a salt include the following compounds.

[0085] However, R is a hydrogen atom or a methyl group, and A －This is a counter anion (derived from acid). The counter anion can be monovalent or polyvalent. Multiple A － They may be the same or different.

[0086] (Unit 33) Unit 33 is a unit based on monomer 33, and monomer 33 is a monomer having an ionic moiety other than monomers 31 and 32 described above. Examples of such monomers include amphoteric monomers. Amphoteric monomers have an anionic moiety and a cationic moiety within the molecule. Examples of amphoteric monomers include sulfobetaine type monomers, carboxybetaine type monomers, and phosphobetaine type monomers, as shown below.

[0087] However, R is either a hydrogen atom or a methyl group.

[0088] (Unit 4) Unit 4 is a unit based on monomer 4, and monomer 4 is a monomer other than monomer 1, monomer 2, and monomer 3. It is preferable that monomer 4 has a polymerizable reactive group. Examples of polymerizable reactive groups include groups having polymerizable carbon-carbon double bonds and hydrolyzable groups, with groups having polymerizable carbon-carbon double bonds being preferred. Examples of groups having polymerizable carbon-carbon double bonds and hydrolyzable groups include X １ Examples of groups similar to those described above are shown, and preferred embodiments are also shown in X １ This is the same as above. Monomer 4 may have two or more polymerizable reactive groups, and these two or more polymerizable reactive groups may be the same or different.

[0089] X １ If the group has a polymerizable carbon-carbon double bond, it is preferable that the polymerizable reactive group of monomer 4 also has a polymerizable carbon-carbon double bond. １ The polymerizable carbon-carbon double bond groups of monomer 4 may be the same or different, but it is preferable that they be the same.

[0090] X １ If the group is hydrolyzable, then the polymerizable reactive group of monomer 4 is also preferably hydrolyzable. １ The hydrolyzable groups of monomer 4 may be the same or different, but they are preferably the same.

[0091] Monomer 4 may have a group that can react with the crosslinking agent described below, in addition to the polymerizable reactive group. Examples of groups that can react with the crosslinking agent include isocyanate groups, blocked isocyanate groups, alkoxysilyl groups, alkoxymethylamide groups, silanol groups, primary amide groups, epoxy groups, hydroxyl groups, urethane groups, urea groups, oxazoline groups, carboxyl groups, sulfonic acid groups, and the like.

[0092] Monomer 4 having a polymerizable carbon-carbon double bond as a polymerizable reactive group includes, but is not limited to, monomers other than monomers 1, 2, and 3, such as vinyl carboxylates, allyl carboxylates, vinyl ethers, allyl ethers, olefin compounds, styrene compounds, (meth)acrylates, (meth)acrylamide compounds, and other vinyl compounds.

[0093] Examples of vinyl carboxylate esters include vinyl acetate, 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.

[0094] 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, and cyclohexyl vinyl ether.

[0095] 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.

[0096] Examples of olefin compounds include alkenes (ethylene, propylene, etc.) and halogenated olefins (vinyl chloride, vinyl fluoride, vinylidene chloride, etc.).

[0097] Examples of styrene-based compounds include styrene, 4-chlorostyrene, pentafluorostyrene, 4-methylstyrene, and 4-methoxystyrene.

[0098] Examples of (meth)acrylates include polyfunctional (meth)acrylates having two or more (meth)acryloyloxy groups, and monofunctional (meth)acrylates having only one (meth)acryloyloxy group. The polyfunctional (meth)acrylate is not particularly limited and is preferably one that has a group that can react with the crosslinking agent described later.Examples of polyfunctional (meth)acrylates include, for example, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, poly(ethylene glycol-propylene glycol) di(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) di(meth)acrylate, poly(propylene glycol-tetramethylene glycol) di(meth)acrylate, diethylene glycol diglycidyl di(meth)acrylate, polyethylene glycol diglycidyl di(meth)acrylate, propylene glycol diglycidyl di(meth)acrylate, polypropylene glycol di(meth)acrylate, and glycerin. Diglycidyl ether di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, glycerin di(meth)acrylate, oxyalkylene glycol mono(meth)acrylate, monoisocyanatoethyl(meth)acrylate, oxyalkylene glycol diisocyanatoethyl(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate Examples include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A di(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, and 2-(((2-((meth)acryloyloxy)ethyl)carbamoyl)oxy)ethyl methacrylate.Commercially available polyfunctional (meth)acrylates include KRM9465 (product name), KRM2000 (product name), KRM8191 (product name), EBECRYL4858 (product name), EBECRYL8402 (product name), EBECRYL8409 (product name), EBECRYL8804 (product name), EBECRYL8807 (product name), and EBECRYL9270 (product name), all of which are polyfunctional urethane acrylates manufactured by Daicel Ornex Co., Ltd. and can be suitably used.

[0099] The monofunctional (meth)acrylate is not particularly limited and is preferably one that has a group that can react with the crosslinking agent described below. Examples of monofunctional (meth)acrylates that do not have a group that can react with the crosslinking agent include alkyl (meth)acrylates (methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, t-butyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, etc.) and alkyl (meth)acrylates having an amide bond (palmitamidepropyl (meth)acrylate, ste Examples of compounds include ethyl meth-acrylate (meth)acrylate, stearamide propyl meth-acrylate, ethyl behenamide acrylate (meth-acrylate), behenamide propyl meth-acrylate (meth-acrylate), aromatic meth-acrylates (phenyl meth-acrylate, benzyl meth-acrylate, pentafluorophenyl meth-acrylate, etc.), aliphatic cyclic meth-acrylates (cyclohexyl meth-acrylate, isobornyl meth-acrylate, etc.), tetrahydrofurfuryl meth-acrylate, and compounds represented below.

[0100] However, R is either a hydrogen atom or a methyl group.

[0101] Examples of monofunctional (meth)acrylates having a group that can react with the crosslinking agent described below include the following compounds: Examples of (meth)acrylates having an isocyanate group include 2-isocyanatoethyl (meth)acrylate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, and 2-(2-acryloyloxyethyloxy)ethyl isocyanate. Examples of (meth)acrylates having a blocked isocyanate group include 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate. Examples of (meth)acrylates having an alkoxysilyl group include 3-((meth)acrylohydrate)propyltrimethoxysilane and 3-[diethoxy(methyl)silyl]propyl (meth)acrylate. Examples of (meth)acrylates having an epoxy group include glycidyl (meth)acrylate and (3,4-epoxycyclohexyl)methyl (meth)acrylate. Examples of (meth)acrylates having a hydroxyl group include 2-hydroxybutyl (meth)acrylate and polyoxypropylene glycol mono(meth)acrylate. Other (meth)acrylates include the compounds shown below.

[0102] However, R is either a hydrogen atom or a methyl group.

[0103] Examples of (meth)acrylamide compounds include polyfunctional (meth)acrylamide compounds having two or more polymerizable reactive groups, and monofunctional (meth)acrylamide compounds having only one polymerizable reactive group. Examples of polyfunctional (meth)acrylamide compounds include N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, and 1,3,5-tri(meth)acryloylhexahydro-1,3,5-triazine.

[0104] Examples of monofunctional (meth)acrylamide compounds include alkyl (meth)acrylamides (N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-diisopropylacrylamide, N-(n-butyl)(meth)acrylamide, N-(t-butyl)(meth)acrylamide, N-lauryl(meth)acrylamide, N-stearyl(meth)acrylamide, N-behenyl(meth)acrylamide, etc.), aromatic (meth)acrylamides (N-phenyl(meth)acrylamide, N-benzyl(meth)acrylamide, etc.), aliphatic cyclic (meth)acrylamides (N-(1-adamantyl)(meth)acrylamide, etc.), hydroxyl-containing (meth)acrylamides ((4-hydroxybutyl)(meth)acrylamide, etc.), and (meth)acrylamides in which the nitrogen atom forms a heterocyclic structure (N-(meth)acryloylmorpholine, N-(meth)acryloylpiperidine, etc.).

[0105] Other vinyl compounds include, for example, trimethylvinylsilane, vinyl (meth)acrylate, and allyl (meth)acrylate.

[0106] Examples of monomers 4 having a hydrolyzable group as a polymerizable reactive group include compounds in which the polymerizable reactive group of monomer 4 having a polymerizable carbon-carbon double bond as described above is substituted with a hydrolyzable group.

[0107] (Composition of Copolymer A) The content of unit 1 relative to the total units constituting copolymer A is, for example, 10 to 90% by mass. The content of unit 2 relative to the total units constituting copolymer A is, for example, 10 to 90% by mass.

[0108] The total content of unit 1, unit 2, and unit 3 relative to all units constituting copolymer A is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and may also be 100% by mass.

[0109] Units 1 to 4 may form a random copolymer or a block copolymer. The units 1 contained in copolymer A may be two or more types. The units 2 contained in copolymer A may be two or more types. The units 3 contained in copolymer A may be two or more types. The units 4 contained in copolymer A may be two or more types.

[0110] The content of fluorine atoms relative to the total mass of copolymer A is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 1% by mass or less, particularly preferably 0.1% by mass or less, and most preferably not containing fluorine atoms. That is, copolymer A is most preferably a non-fluorine copolymer. The content of fluorine atoms relative to the total mass of copolymer A can be measured by a combustion ion chromatography method or the like.

[0111] The content of each unit １ can be calculated from the reaction rates of monomers 1 to 4 by H-NMR, gas chromatography, and high performance liquid chromatography.

[0112] The Mn of copolymer A is preferably from 1,000 to 1,000,000, more preferably from 10,000 to 1,000,000, and still more preferably from 10,000 to 800,000. When the Mn of copolymer A is at least the above lower limit, the oil repellency of the article treated with copolymer A is more excellent. When the Mn of copolymer A is at most the above upper limit, the dispersibility in various solvents is more excellent.

[0113] The Mw of copolymer A is preferably from 1,000 to 1,000,000, more preferably from 10,000 to 1,000,000, and still more preferably from 10,000 to 800,000. When the Mw of copolymer A is at least the above lower limit, the oil repellency of the article treated with copolymer A is more excellent. When the Mw of copolymer A is at most the above upper limit, the dispersibility in various solvents is more excellent.

[0114] (Composition of Copolymer A1) In one embodiment of the present disclosure, the oil-repellent composition preferably includes, for example, a copolymer having unit 1, unit 2, and unit 3 (hereinafter also referred to as "copolymer A1") as copolymer A. In particular, copolymer A1 dissolves or disperses well in non-aqueous media as described later and is excellent in imparting oil repellency (oil resistance) when a porous body (porous resin, porous fiber, etc.) described later is treated with it. In this case, the content of unit 1 relative to the total units constituting copolymer A1 is preferably 15% by mass or more, 20% by mass or more, 25% by mass or more, more than 25% by mass, 30% by mass or more, or 35% by mass or more, from the viewpoint of oil repellency (oil resistance) when a porous body described later is treated with it. Also, 90% by mass or less, 85% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, less than 50% by mass, or 45% by mass or less is preferred. The upper and lower limits can be combined as appropriate. For example, the content of unit 1 relative to the total units constituting copolymer A1 is preferably 15 to 90% by mass, more preferably 20 to 85% by mass, even more preferably 25 to 80% by mass, particularly preferably more than 25% by mass and 70% by mass or less, and most preferably 30% to 45% by mass.

[0115] The content of unit 2 relative to the total units constituting copolymer A1 is preferably 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, or more than 50% by mass, from the viewpoint of oil repellency (oil resistance) when the porous body described later is treated. Also, 80% by mass or less, 75% by mass or less, 70% by mass or less, or 60% by mass or less are preferred. The upper and lower limits can be combined as appropriate. For example, the content of unit 2 relative to the total units constituting copolymer A1 is preferably 5 to 80% by mass, more preferably 7 to 75% by mass, even more preferably 10 to 70% by mass, even more preferably 20 to 70% by mass, particularly preferably 40 to 60% by mass, and most preferably more than 50% by mass and 60% by mass or less.

[0116] The content of unit 3 relative to the total units constituting copolymer A1 is preferably more than 0% by mass and less than 29% by mass, more preferably 1 to 27% by mass, even more preferably 2 to 25% by mass, and particularly preferably 4 to 20% by mass. When the content of unit 3 is below the above upper limit, the water resistance of the coated article is better. When the content of unit 3 is above the above lower limit, the oil resistance of the coated article is better.

[0117] When copolymer A1 contains unit 31 as unit 3, for example, from the viewpoint of oil repellency (oil resistance) when the porous body described later is treated, the content of unit 31 is preferably more than 0% by mass and less than 29% by mass, 0.1 to 20% by mass, 0.5 to 15% by mass, 1 to 10% by mass, 1 to 6% by mass, or 2 to 6% by mass.

[0118] When copolymer A1 contains unit 32 as unit 3, for example, from the viewpoint of oil repellency (oil resistance) when the porous body described later is treated, the content of unit 32 is preferably more than 0% by mass and less than 29% by mass, 0.1 to 25% by mass, 5 to 20% by mass, 10 to 18% by mass, or 14 to 18% by mass.

[0119] The total content of units 2 and 3 relative to the total number of units constituting copolymer A1 is preferably 10 to 85% by mass, more preferably 15 to 80% by mass, and even more preferably 20 to 75% by mass. Even if some or all of the ion-donating groups of unit 3 are ionized to form a salt, the content of unit 3 is calculated by converting it to the non-ionized state (unit 3 having ion-donating groups before ionization). Copolymer A1 may further contain unit 4. Copolymer A1 may consist of units 1, 2, and 3.

[0120] (Composition of Copolymer A2) In one embodiment of the present disclosure, the oil-repellent composition preferably contains, for example, a copolymer A consisting of unit 1, unit 2, and optionally unit 4 (hereinafter also referred to as "copolymer A2"). In this case, the content of unit 1 relative to the total units constituting copolymer A2 is preferably 10 to 55% by mass, more preferably 15 to 53% by mass, even more preferably 20 to 48% by mass, and particularly preferably 25 to 43% by mass. The content of unit 2 relative to the total units constituting copolymer A2 is preferably 45 to 90% by mass, more preferably 47 to 85% by mass, even more preferably 52 to 80% by mass, and particularly preferably 57 to 75% by mass. Copolymer A2 may consist of unit 1 and unit 2.

[0121] (Composition of Copolymer A3) In one embodiment of the present disclosure, the oil-repellent composition preferably includes, for example, a copolymer having unit 1, unit 2, and unit 31 (hereinafter also referred to as "copolymer A3") as copolymer A. Since copolymer A3 has excellent water dispersibility, when the oil-repellent composition contains a liquid medium described later, and the liquid medium is an aqueous medium (preferably water, more preferably water with a pH greater than 7.0 at 25°C), the oil-repellent composition can be obtained as an aqueous dispersion in which copolymer A3 is well dispersed.

[0122] The content of unit 1 relative to all units constituting copolymer A3 is preferably 10% by mass or more, 20% by mass or more, 25% by mass or more, greater than 25% by mass, 30% by mass or more, greater than 30% by mass, 35% by mass or more, or greater than 35% by mass, for example, from the viewpoint of oil repellency to high-temperature oil. Also, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, less than 50% by mass, 45% by mass or less, or less than 45% by mass. The above upper and lower limits can be combined as appropriate. The content of unit 1 relative to all units constituting copolymer A3 is preferably 10 to 90% by mass, 25 to 80% by mass, greater than 25% by mass and 60% by mass or less, 30 to 50% by mass, greater than 30% by mass and less than 50% by mass, or 35 to 45% by mass, for example, from the viewpoint of oil repellency (oil resistance) to high-temperature oil.

[0123] The content of unit 2 relative to all units constituting copolymer A3 is preferably 10% by mass or more, more than 10% by mass, 20% by mass or more, more than 20% by mass, 25% by mass or more, more than 25% by mass, 30% by mass or more, more than 30% by mass, 35% by mass or more, more than 35% by mass, 40% by mass or more, more than 40% by mass, 45% by mass or more, more than 45% by mass, 50% by mass or more, and more than 50% by mass, from the viewpoint of oil repellency (oil resistance) to high-temperature oils. Also, 90% by mass or less, 80% by mass or less, 70% by mass or less, and 60% by mass or less are preferred. The above upper and lower limits can be combined as appropriate. The content of unit 2 relative to all units constituting copolymer A3 is preferably 10 to 90% by mass, 20 to 80% by mass, 30 to 70% by mass, 40 to 70% by mass, 45 to 60% by mass, and 50 to 60% by mass, from the viewpoint of oil repellency (oil resistance) to high-temperature oils.

[0124] The content of unit 31 relative to the total units constituting copolymer A3 is preferably more than 0% by mass, 0.1% or more by mass, 0.5% or more by mass, 1% or more by mass, 2% or more by mass, or 3% or more by mass, for example, from the viewpoint of oil repellency (oil resistance) to high-temperature oils. Also, less than 29% by mass, 20% or less by mass, 15% or less by mass, 10% or less by mass, 6% or less by mass, or 5% or less by mass. The above upper and lower limits can be combined as appropriate. The content of unit 31 relative to the total units constituting copolymer A3 is preferably more than 0% by mass and less than 29% by mass, 0.1 to 20% by mass, 0.5 to 15% by mass, 1 to 10% by mass, 1 to 6% by mass, 2 to 6% by mass, or 2 to 4% by mass, for example, from the viewpoint of oil repellency (oil resistance) to high-temperature oils. Even if some or all of the anion-donating groups of unit 31 are ionized to form a salt, the content of unit 31 is calculated by converting it to the non-ionized state (unit 31 with anion-donating groups before ionization).

[0125] Copolymer A3 may preferably not have unit 32, and may preferably consist of unit 1, unit 2, unit 31 and optionally unit 4, and may also preferably consist of unit 1, unit 2 and unit 31.

[0126] The total content of unit 1, unit 2, and unit 31 relative to the total units constituting copolymer A3 is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, even more preferably 99 to 100% by mass, and particularly preferably 100% by mass. The total content of unit 1 and unit 31 relative to the total units constituting copolymer A3 is preferably 30 to 80% by mass, more preferably 35 to 60% by mass, and even more preferably 40 to 50% by mass. The total content of unit 2 and unit 31 relative to the total units constituting copolymer A3 is preferably 20 to 80% by mass, and more preferably 50 to 70% by mass.

[0127] The percentage (mol%) of unit 1 relative to the total number of units constituting copolymer A3 is M Ａ１ The percentage of unit 2 (mol%) is M Ａ２ When that happens, M Ａ２ / M Ａ１ For example, from the viewpoint of oil repellency (oil resistance) to high-temperature oil, values ​​of 2.3 or higher, 2.5 or higher, 3.0 or higher, and 4.0 or higher are preferred. Also, values ​​of 7.0 or lower, 6.0 or lower, 5.5 or lower, 5.3 or lower, and 5.0 or lower are preferred. The above upper and lower limits can be combined as appropriate. M in copolymer A3 Ａ２ / M Ａ１ For example, from the viewpoint of oil repellency (oil resistance) to high-temperature oil, values ​​of 2.3 to 7.0, 2.5 to 6.0, 3.0 to 5.5, 4.0 to 5.3, and 4.0 to 5.0 are preferred.

[0128] The percentage (mol%) of unit 2 relative to the total number of units constituting copolymer A3 is M Ａ２ The content percentage (mol%) of unit 31 is M Ａ３１ When that happens, M Ａ２ / M Ａ３１ For example, from the viewpoint of oil repellency (oil resistance) to high-temperature oil, values ​​of 3.5 or higher, 4.0 or higher, 4.5 or higher, 5.0 or higher, 6.0 or higher, 6.5 or higher, 7.0 or higher, 7.5 or higher, and 8.0 or higher are preferred. Also, values ​​of 11.0 or lower, 10.5 or lower, 10.0 or lower, and 9.5 or lower are preferred. The above upper and lower limits can be combined as appropriate. M in copolymer A3 Ａ２ / M Ａ３１For example, from the viewpoint of oil repellency (oil resistance) to high-temperature oil, values ​​of 3.5 to 11.0, 4.5 to 10.5, 5.0 to 10.0, 6.0 to 10.0, 7.0 to 10.0, and 7.5 to 9.5 are preferred.

[0129] (Composition of Copolymer A4) In one embodiment of the present disclosure, the oil-repellent composition preferably includes, for example, a copolymer having unit 1, unit 2, and unit 32 (hereinafter also referred to as "copolymer A4") as copolymer A. Since copolymer A4 has excellent water dispersibility, when the oil-repellent composition contains a liquid medium described later, and the liquid medium is an aqueous medium (preferably water, more preferably water with a pH of less than 7.0 at 25°C), the oil-repellent composition can be obtained as an aqueous dispersion in which copolymer A4 is well dispersed.

[0130] The content of unit 1 relative to all units constituting copolymer A4 is preferably 10% by mass or more, 20% by mass or more, 25% by mass or more, greater than 25% by mass, 30% by mass or more, greater than 30% by mass, 35% by mass or more, or greater than 35% by mass, from the viewpoint of oil repellency to high-temperature oils. Also, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, less than 50% by mass, 45% by mass or less, or less than 45% by mass. The above upper and lower limits can be combined as appropriate. The content of unit 1 relative to all units constituting copolymer A4 is preferably 10 to 90% by mass, 25 to 80% by mass, greater than 25% by mass and 60% by mass or less, 30 to 50% by mass, greater than 30% by mass and less than 50% by mass, or 35 to 45% by mass, from the viewpoint of oil repellency (oil resistance) to high-temperature oils.

[0131] The content of unit 2 relative to all units constituting copolymer A4 is preferably 10% by mass or more, more than 10% by mass, 20% by mass or more, more than 20% by mass, 25% by mass or more, more than 25% by mass, 30% by mass or more, more than 30% by mass, 35% by mass or more, more than 35% by mass, 40% by mass or more, more than 40% by mass, 45% by mass or more, more than 45% by mass, 50% by mass or more, and more than 50% by mass, from the viewpoint of oil repellency (oil resistance) to high-temperature oils. Also, 90% by mass or less, 80% by mass or less, 70% by mass or less, and 60% by mass or less are preferred. The above upper and lower limits can be combined as appropriate. The content of unit 2 relative to all units constituting copolymer A4 is preferably 10 to 90% by mass, 20 to 80% by mass, 30 to 70% by mass, 40 to 70% by mass, 45 to 60% by mass, and 50 to 60% by mass, from the viewpoint of oil repellency (oil resistance) to high-temperature oils.

[0132] The content of unit 32 relative to the total units constituting copolymer A4 is preferably greater than 0% by mass, 0.1% or more by mass, 1% or more by mass, 5% or more by mass, 7% or more by mass, or 9% or more by mass, for example from the viewpoint of oil repellency (oil resistance) to high-temperature oils. Also, less than 29% by mass, 20% or less by mass, 15% or less by mass, 12% or less by mass, or 10% or less by mass. The above upper and lower limits can be combined as appropriate. The content of unit 32 relative to the total units constituting copolymer A4 is preferably greater than 0% by mass and less than 29% by mass, 0.1 to 20% by mass, 1 to 15% by mass, 5 to 12% by mass, or 7 to 12% by mass, for example from the viewpoint of oil repellency (oil resistance) to high-temperature oils. Even when some or all of the cation donor groups of unit 32 are ionized to form a salt, the content of unit 32 is calculated by converting it to the non-ionized state (unit 32 having cation donor groups before ionization).

[0133] Copolymer A4 may preferably not have unit 31, and may preferably consist of unit 1, unit 2, unit 32 and optionally unit 4, and may also preferably consist of unit 1, unit 2 and unit 32.

[0134] The total content of unit 1, unit 2, and unit 32 relative to the total units constituting copolymer A4 is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, even more preferably 99 to 100% by mass, and particularly preferably 100% by mass. The total content of unit 1 and unit 32 relative to the total units constituting copolymer A4 is preferably 30 to 80% by mass, more preferably 35 to 60% by mass, and even more preferably 40 to 50% by mass. The total content of unit 2 and unit 32 relative to the total units constituting copolymer A4 is preferably 20 to 80% by mass, and more preferably 50 to 70% by mass.

[0135] The percentage (mol%) of unit 1 relative to all units constituting copolymer A4 is M Ａ１ The percentage of unit 2 (mol%) is M Ａ２ When that happens, M Ａ２ / M Ａ１ For example, from the viewpoint of oil repellency (oil resistance) to high-temperature oil, values ​​of 1.2 or higher, 1.5 or higher, 3.0 or higher, and 4.0 or higher are preferred. Also, values ​​of 5.2 or lower and 5.0 or lower are preferred. The above upper and lower limits can be combined as appropriate. M in copolymer A4 Ａ２ / M Ａ１ For example, from the viewpoint of oil repellency (oil resistance) to high-temperature oil, values ​​of 1.2 to 5.2, 1.5 to 5.2 to 5.2, 3.0 to 5.2, 4.0 to 5.2, and 4.0 to 5.0 are preferred.

[0136] The percentage (mol%) of unit 2 relative to the total number of units constituting copolymer A4 is M Ａ２ The content percentage (mol%) of unit 32 is M Ａ３２ When that happens, M Ａ２ / M Ａ３２ For example, from the viewpoint of oil repellency (oil resistance) to high-temperature oils, values ​​of 3.5 or higher, 4.0 or higher, 4.5 or higher, 5.0 or higher, and 6.0 or higher are preferred. Also, values ​​of 11.0 or lower, 10.0 or lower, 9.0 or lower, 8.0 or lower, and 7.0 or lower are preferred. The above upper and lower limits can be combined as appropriate. M in copolymer A4 Ａ２ / M Ａ３２ For example, from the viewpoint of oil repellency (oil resistance) to high-temperature oils, values ​​of 3.5 to 11.0, 4.5 to 10.0, 5.0 to 9.0, and 6.0 to 8.0 are preferred.

[0137] <Copolymer B> Copolymer B contains unit 1, unit 32, and unit 31. Units that correspond to either monomer 32 or monomer 31 are treated as unit 1. By combining unit 1, unit 32, and unit 31, it is believed that the oil repellency of articles treated with the oil-repellent composition containing copolymer B will be further improved. Furthermore, if the article is oil-resistant paper, it is believed that the defoaming properties of the composition will be improved due to the improved viscosity of the composition, and that the workability in the oil-resistant treatment process will be improved. In addition, it is believed that the oil resistance to high-temperature oils (when a load is applied), such as corn oil, will be improved, and the resistance to a wide range of pH will be improved.

[0138] Copolymer B may further contain units (unit 2, unit 4) based on monomers other than monomer 1, monomer 32, and monomer 31. Monomer 1 and unit 1, monomer 2 and unit 2, monomer 3 and unit 3, monomer 4 and unit 4 are the same as those detailed in copolymer A above, and the preferred embodiments are also the same.

[0139] (Composition of Copolymer B) The content of unit 1 relative to the total units constituting copolymer B is preferably, for example, 10% by mass or more, 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. The content of unit 1 relative to the total units constituting copolymer B is preferably, for example, 90% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, less than 50% by mass, or 45% by mass or less. The above upper and lower limits can be combined as appropriate. For example, the content of unit 1 relative to the total units constituting copolymer B is preferably 10 to 90% by mass, 15 to 90% by mass, 20 to 85% by mass, 25 to 80% by mass, more preferably 30 to 75% by mass, even more preferably 35 to 60% by mass, even more preferably 35 to 50% by mass, particularly preferably 35% by mass or more and less than 50% by mass, and most preferably 40 to 45% by mass.

[0140] The content of unit 32 relative to the total units constituting copolymer B is preferably, for example, greater than 0% by mass, 0.1% by mass or more, 0.5% by mass or more, 1.0% by mass or more, 2.5% by mass or more, 5.0% by mass or more, 7.5% by mass or more, 10% by mass or more, 12.5% ​​by mass or more, 15% by mass or more, or 17.5% by mass or more. The content of unit 32 relative to the total units constituting copolymer B is preferably, for example, 50% by mass or less, 40% by mass or less, 30% by mass or less, less than 29% by mass, 27% by mass or less, 20% by mass or less, 17.5% by mass or less, 15% by mass or less, 12.5% ​​by mass or less, 10% by mass or less, 7.5% by mass or less, 5.0% by mass or less, 2.5% by mass or less, or 1.0% by mass or less. The above upper and lower limits can be combined as appropriate. For example, the content of unit 32 relative to the total units constituting copolymer B is preferably 0.1 to 50% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 12.5% ​​by mass, and particularly preferably 0.5 to 2.5% by mass or 10 to 12.5% ​​by mass.

[0141] The content of unit 31 relative to the total units constituting copolymer B is preferably, for example, more than 0% by mass, 0.1% by mass or more, 0.5% by mass or more, 1.0% by mass or more, 1.5% by mass or more, 2.0% by mass or more, 2.5% by mass or more, 3.0% by mass or more, 3.5% by mass or more, 4.0% by mass or more, or 4.5% by mass or more. The content of unit 31 relative to the total units constituting copolymer B is preferably, for example, 50% by mass or less, 30% by mass or less, less than 29% by mass, 27% by mass or less, 25% by mass or less, 20% by mass or less, 10% by mass or less, 5.0% by mass or less, 4.5% by mass or less, 4.0% by mass or less, 3.5% by mass or less, 3.0% by mass or less, 2.5% by mass or less, 2.0% by mass or less, 1.5% by mass or less, or 1.0% by mass or less. The above upper and lower limits can be combined as appropriate. For example, the content of unit 31 relative to the total units constituting copolymer B is preferably more than 0% by mass and 50% by mass or less, more preferably more than 0% by mass and less than 29% by mass, more preferably 0.1 to 10% by mass, even more preferably 0.5 to 5.0% by mass, and particularly preferably 0.5 to 2.5% by mass or 3.5 to 4.5% by mass.

[0142] The total content of units 32 and 31 relative to the total units constituting copolymer B is preferably 1.0 to 25% by mass, and more preferably 2.0 to 15% by mass.

[0143] The total content of unit 1, unit 32, and unit 31 relative to the total units constituting copolymer B is preferably 20 to 90% by mass, more preferably 40 to 60% by mass, and even more preferably 45 to 55% by mass.

[0144] In copolymer B, the mass ratio of the content of unit 1 to the total content of unit 32 and unit 31 is preferably 1.0 to 15.0, more preferably 2.0 to 12.0, even more preferably 3.0 to 10.0, and particularly preferably 3.3 to 8.0.

[0145] When copolymer B contains unit 2, the content of unit 2 relative to the total units constituting copolymer B is preferably, for example, 1% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, more than 50% by mass, or 55% by mass or more. When copolymer B contains unit 2, the content of unit 2 relative to the total units constituting copolymer B is preferably, for example, 80% by mass or less, 75% by mass or less, 70% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, or 25% by mass or less. When copolymer B contains unit 2, the content of unit 2 relative to the total units constituting copolymer B is preferably 1 to 80% by mass, 5 to 80% by mass, 7 to 75% by mass, more preferably 10 to 70% by mass, even more preferably 30 to 60% by mass, particularly preferably 40 to 60% by mass, and particularly preferably 45% by mass or more but less than 50% by mass or more than 50% by mass and 60% by mass or less.

[0146] When copolymer B contains unit 2, the total content of unit 32, unit 31, and unit 2 relative to the total units constituting copolymer B1 is preferably, for example, 10% by mass or more, 15% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more. When copolymer B contains unit 2, the total content of unit 32, unit 31, and unit 2 relative to the total units constituting copolymer B1 is preferably, for example, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, or 65% by mass or less. When copolymer B contains unit 2, the total content of unit 32, unit 31, and unit 2 relative to the total units constituting copolymer B1 is preferably 10 to 85% by mass, more preferably 15 to 80% by mass, even more preferably 20 to 75% by mass, particularly preferably 40 to 70% by mass, and most preferably 55 to 65% by mass.

[0147] When copolymer B contains unit 2, the total content of unit 1, unit 32, unit 31, and unit 2 relative to all units constituting copolymer B1 is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 99% by mass or more, and particularly preferably 100% by mass.

[0148] When copolymer B contains unit 2, the mass ratio of the content of unit 1 to the total content of unit 32, unit 31, and unit 2 in copolymer B is preferably 0.1 to 3.0, more preferably 0.3 to 2.5, even more preferably 0.5 to 2.0, and particularly preferably 0.7 to 1.0.

[0149] Even if some or all of the ion-donating groups of unit 32 or unit 31 are ionized to form a salt, the content of unit 32 and unit 31 is calculated by converting them to their non-ionized state (unit 32 and unit 31 with ion-donating groups before ionization).

[0150] Copolymer B may further contain unit 4. When copolymer B further contains unit 4, the content of unit 4 relative to the total units constituting copolymer B is preferably greater than 0% by mass and 10% by mass or less, more preferably greater than 0% by mass and 5% by mass or less, even more preferably greater than 0% by mass and 1% by mass or less, and particularly preferably greater than 0% by mass and 0.1% by mass or less.

[0151] The total content of unit 1, monomer 32, monomer 31, and unit 4 relative to all units constituting copolymer B is preferably more than 90% by mass, more preferably 95% by mass or more, and may be 100% by mass.

[0152] Units 1, 32, 31, 2, and 4 may form random copolymers or block copolymers. Copolymer B may contain two or more types of unit 1. Copolymer B may contain two or more types of monomer 32. Copolymer B may contain two or more types of monomer 31. Copolymer B may contain two or more types of unit 2. Copolymer B may contain two or more types of unit 4.

[0153] The fluorine atom content of copolymer B relative to its total mass is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 1% by mass or less, particularly preferably 0.1% by mass or less, and most preferably no fluorine atoms at all. In other words, copolymer B is most preferably a non-fluorine copolymer. The fluorine atom content relative to the total mass of copolymer B can be measured by methods such as combustion ion chromatography.

[0154] The content of each unit is: １ This can be calculated by the reaction rates of monomers 1-4 obtained by H-NMR, gas chromatography, and high-performance liquid chromatography.

[0155] The manganese (Mn) of copolymer B 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 B is above the lower limit, the oil repellency of the article treated with copolymer B is better. When the Mn of copolymer B is below the upper limit, the dispersibility in various solvents is better.

[0156] The Mw of copolymer B 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 B is above the lower limit, the oil repellency of the article treated with copolymer B is better. When the Mw of copolymer B is below the upper limit, the dispersibility in various solvents is better.

[0157] (Composition of Copolymer B1) Copolymer B1 is also preferred as copolymer B. Copolymer B1 has units 1, 2, 31 and 32. Copolymer B1 is considered to have excellent oil repellency when copolymer B is dispersed in an aqueous medium with a pH greater than 7.0 at 25°C and used as an aqueous dispersion, or when it is dissolved or dispersed in a non-aqueous medium and used to treat a porous body described later.

[0158] The content of unit 1 relative to the total units constituting copolymer B1 is the same as that of copolymer B described above, and the preferred embodiment is also the same.

[0159] The content of unit 32 relative to the total units constituting copolymer B1 is preferably, for example, greater than 0% by mass, 0.1% by mass or more, 0.5% by mass or more, or 1.0% by mass or more. The content of unit 32 relative to the total units constituting copolymer B1 is preferably, for example, less than 29% by mass, 15% by mass or less, 10% by mass or less, 5.0% by mass or less, or 2.0% by mass or less. The above upper and lower limits can be combined as appropriate. For example, the content of unit 32 relative to the total units constituting copolymer B1 is preferably greater than 0% by mass and less than 29% by mass, more preferably 0.1 to 15% by mass, even more preferably 0.5 to 10% by mass, particularly preferably 0.5 to 5.0% by mass, and most preferably 0.5 to 2.0% by mass.

[0160] The content of unit 31 relative to the total units constituting copolymer B1 is preferably, for example, greater than 0% by mass, 1.0% by mass or more, 2.0% by mass or more, or 3.0% by mass or more. The content of unit 31 relative to the total units constituting copolymer B1 is preferably, for example, less than 29% by mass, 10% by mass or less, 8.0% by mass or less, 5.0% by mass or less, or 4.0% by mass or less. The above upper and lower limits can be combined as appropriate. For example, the content of unit 31 relative to the total units constituting copolymer B1 is preferably greater than 0% by mass and less than 29% by mass, more preferably 1.0 to 10% by mass, even more preferably 2.0 to 8.0% by mass, particularly preferably 3.0 to 5.0% by mass, and most preferably 3.0 to 4.0% by mass.

[0161] The total content of units 32 and 31 relative to the total units constituting copolymer B1 is preferably 1 to 25% by mass, more preferably 2 to 15% by mass, even more preferably 3 to 10% by mass, and particularly preferably 4 to 8% by mass.

[0162] The total content of unit 1, unit 32, and unit 31 relative to the total units constituting copolymer B1 is preferably 20 to 90% by mass, more preferably 40 to 60% by mass, and even more preferably 40 to 50% by mass.

[0163] In copolymer B1, the mass ratio of the content of unit 1 to the total content of unit 32 and unit 31 is preferably 1.0 to 15.0, more preferably 2.0 to 12.0, even more preferably 3.0 to 10.0, and particularly preferably 6.0 to 9.0.

[0164] From the viewpoint of oil-repellent stability, the content of unit 2 relative to the total units constituting copolymer B1 is preferably, for example, 1% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, or more than 50% by mass. From the viewpoint of oil-repellent stability, the content of unit 2 relative to the total units constituting copolymer B1 is preferably, for example, 80% by mass or less, 70% by mass or less, or 60% by mass or less. The above upper and lower limits can be combined as appropriate. For example, from the viewpoint of oil-repellent stability, the content of unit 2 relative to the total units constituting copolymer B1 is preferably 1 to 80% by mass, 10 to 70% by mass, 30 to 70% by mass, 40 to 70% by mass, 50 to 70% by mass, 50 to 60% by mass, or more than 50% by mass and 60% by mass or less.

[0165] The total content of units 32, 31, and 2 relative to all units constituting copolymer B1 is preferably, for example, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, or 55% by mass or more. The total content of units 32, 31, and 2 relative to all units constituting copolymer B1 is preferably, for example, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, or 65% by mass or less. The upper and lower limits can be combined as appropriate. For example, the total content of units 32, 31, and 2 relative to all units constituting copolymer B1 is preferably 10 to 85% by mass, more preferably 20 to 75% by mass, even more preferably 40 to 70% by mass, particularly preferably 50 to 70% by mass, and most preferably 55 to 65% by mass.

[0166] The total content of unit 1, unit 32, unit 31, and unit 2 relative to the total units constituting copolymer B1 is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 99% by mass or more, and particularly preferably 100% by mass.

[0167] In copolymer B2, the mass ratio of the content of unit 1 to the total content of unit 32, unit 31, and unit 2 is preferably 0.1 to 3.0, more preferably 0.3 to 2.5, even more preferably 0.5 to 2.0, and particularly preferably 0.6 to 1.0.

[0168] The percentage (mol%) of unit 1 relative to the total number of units constituting copolymer B1 is M Ｂ１ The percentage of unit 2 (mol%) is M Ｂ２ When that happens, M Ｂ２ / M Ｂ１ For example, values ​​of 1.0 or higher, 2.0 or higher, 3.0 or higher, and 4.0 or higher are preferred. Also, values ​​of 9.0 or lower, 8.0 or lower, 7.0 or lower, 6.0 or lower, and 5.0 or lower are preferred. The upper and lower limits can be combined as appropriate. M in copolymer B1 Ｂ２ / M Ｂ１ For example, values ​​of 1.0-9.0, 2.0-8.0, 3.0-7.0, 4.0-6.0, and 4.0-5.0 are preferred.

[0169] In copolymer B1, the content ratio (mass%) of unit 31 is W Ｂ３１ The percentage of the content of unit 32 (mass%) is W Ｂ３２ When that happens, W Ｂ３２ / W Ｂ３１ For example, values ​​of 2.0 or less, 1.5 or less, 1.0 or less, less than 1.0, 0.8 or less, 0.5 or less, and 0.4 or less are preferred. Also, values ​​greater than 0 and 0.1 or greater are preferred. The upper and lower limits can be combined as appropriate. For example, W in copolymer B1 Ｂ３２ / W Ｂ３１ The following ranges are preferable: greater than 0 and less than or equal to 2.0, greater than 0 and less than or equal to 1.5, greater than 0 and less than 1.0, 0.1 to 0.8, 0.1 to 0.5, and 0.1 to 0.4.

[0170] In copolymer B1, the content ratio (mass%) of unit 2 is W ２ The percentage of the content of unit 31 (mass%) is W Ｂ３１ When that happens, W ２ / W Ｂ３１ For example, values ​​of 9.0 or higher, 10.0 or higher, 11.0 or higher, 12.0 or higher, and 13.0 or higher are preferred. Also, values ​​of 25.0 or lower, 20.0 or lower, and 15.0 or lower are preferred. The upper and lower limits can be combined as appropriate. For example, W in copolymer B1 ２ / W Ｂ３１ The following are preferred: 9.0–25.0, 11.0–20.0, and 13.0–15.0.

[0171] (Composition of Copolymer B2) Copolymer B2 is also preferred as copolymer B. Copolymer B2 has units 1, 2, 31 and 32. Copolymer B2 is considered to have excellent oil repellency when copolymer B is dispersed in an aqueous medium with a pH of less than 7.0 at 25°C and used as an aqueous dispersion, or when it is dissolved or dispersed in a non-aqueous medium and used to treat porous bodies described later.

[0172] The content of unit 1 relative to the total units constituting copolymer B2 is the same as that of copolymer B described above, and the preferred embodiment is also the same.

[0173] The content of unit 32 relative to the total units constituting copolymer B2 is preferably, for example, greater than 0% by mass, 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 2.5% by mass or more, 5% by mass or more, or 7.5% by mass or more. The content of unit 32 relative to the total units constituting copolymer B2 is preferably, for example, less than 29% by mass, 27% by mass or less, 20% by mass or less, 17.5% by mass or less, 15% by mass or less, or 12.5% ​​by mass or less. The above upper and lower limits can be combined as appropriate. For example, the content of unit 32 relative to the total units constituting copolymer B2 is preferably greater than 0% by mass and less than 29% by mass, more preferably 5 to 27% by mass, even more preferably 7.5 to 20% by mass, and particularly preferably 7.5 to 12.5% ​​by mass.

[0174] The content of unit 31 relative to the total units constituting copolymer B2 is preferably, for example, more than 0% by mass, 0.1% by mass or more, 0.5% by mass or more, 1.0% by mass or more, or 1.5% by mass or more. The content of unit 31 relative to the total units constituting copolymer B2 is preferably, for example, less than 29% by mass, 10% by mass or less, 5.0% by mass or less, 4.5% by mass or less, 4.0% by mass or less, 3.5% by mass or less, 3.0% by mass or less, 2.5% by mass or less, or 2.0% by mass or less. The above upper and lower limits can be combined as appropriate. For example, the content of unit 31 relative to the total units constituting copolymer B2 is preferably more than 0% by mass and less than 29% by mass, more preferably 0.1 to 10% by mass, even more preferably 0.5 to 5.0% by mass, particularly preferably 0.5 to 2.5% by mass, and most preferably 1.0 to 2.0% by mass.

[0175] The total content of units 32 and 31 relative to the total units constituting copolymer B2 is preferably 1 to 25% by mass, more preferably 2 to 15% by mass, even more preferably 5 to 15% by mass, and particularly preferably 10 to 15% by mass.

[0176] The total content of unit 1, unit 32, and unit 31 relative to all units constituting copolymer B2 is preferably 20 to 90% by mass, more preferably 40 to 60% by mass, and even more preferably 45 to 55% by mass.

[0177] In copolymer B2, the mass ratio of the content of unit 1 to the total content of unit 32 and unit 31 is preferably 1.0 to 15.0, more preferably 2.0 to 12.0, even more preferably 3.0 to 10.0, and particularly preferably 3.0 to 4.5.

[0178] The content of unit 2 relative to the total units constituting copolymer B2 is preferably, for example, 1% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 45% by mass or more, from the viewpoint of oil-repellent stability. The content of unit 2 relative to the total units constituting copolymer B2 is preferably, for example, 80% by mass or less, 70% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, or less than 50% by mass, from the viewpoint of oil-repellent stability. The above upper and lower limits can be combined as appropriate. For example, from the viewpoint of oil-repellent stability, the content of unit 2 relative to the total units constituting copolymer B2 is preferably 1 to 80% by mass, 10 to 70% by mass, 30 to 60% by mass, 40 to 60% by mass, 40% by mass or more and less than 50% by mass, or 45% by mass or more and less than 50% by mass.

[0179] The total content of units 32, 31, and 2 relative to all units constituting copolymer B2 is preferably, for example, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, or 55% by mass or more. The total content of units 32, 31, and 2 relative to all units constituting copolymer B2 is preferably, for example, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, or 65% by mass or less. The upper and lower limits can be combined as appropriate. For example, the total content of units 32, 31, and 2 relative to all units constituting copolymer B2 is preferably 10 to 85% by mass, more preferably 20 to 75% by mass, even more preferably 40 to 70% by mass, particularly preferably 50 to 70% by mass, and most preferably 55 to 65% by mass.

[0180] The total content of unit 1, unit 32, unit 31, and unit 2 relative to the total units constituting copolymer B2 is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 99% by mass or more, and particularly preferably 100% by mass.

[0181] In copolymer B2, the mass ratio of the content of unit 1 to the total content of unit 32, unit 31, and unit 2 is preferably 0.1 to 3.0, more preferably 0.3 to 2.5, even more preferably 0.5 to 2.0, and particularly preferably 0.7 to 1.0.

[0182] The percentage (mol%) of unit 1 relative to the total number of units constituting copolymer B2 is M Ｂ１ The percentage of unit 2 (mol%) is M Ｂ２ When that happens, M Ｂ２ / M Ｂ１ For example, values ​​of 1.0 or higher, 2.0 or higher, 3.0 or higher, and 4.0 or higher are preferred. Also, values ​​of 9.0 or lower, 8.0 or lower, 7.0 or lower, 6.0 or lower, 5.0 or lower, and 4.0 or lower are preferred. The upper and lower limits can be combined as appropriate. M in copolymer B2 Ｂ２ / M Ｂ１ For example, values ​​of 1.0 to 9.0, 2.0 to 8.0, 3.0 to 7.0, 3.0 to 6.0, 3.0 to 5.0, and 3.0 to 4.0 are preferred.

[0183] In copolymer B2, the content ratio (mass%) of unit 31 is WＢ３１ The percentage of the content of unit 32 (mass%) is W Ｂ３２ When that happens, W Ｂ３２ / W Ｂ３１ For example, values ​​greater than 2.0, 3.0 or more, 4.0 or more, 5.0 or more, and 6.0 or more are preferred. Also, values ​​of 9.0 or less, 8.0 or less, and 7.0 or less are preferred. The upper and lower limits can be combined as appropriate. For example, W in copolymer B2 Ｂ３２ / W Ｂ３１ Preferably, the values ​​are greater than 2.0 and less than or equal to 9.0, 3.0 to 9.0, 4.0 to 9.0, 5.0 to 8.0, and 6.0 to 7.0.

[0184] In copolymer B2, the content ratio (mass%) of unit 2 is W ２ The percentage of the content of unit 32 (mass%) is W Ｂ３２ When that happens, W ２ / W Ｂ３２ For example, values ​​of 2.8 or higher, 3.0 or higher, 3.5 or higher, 4.0 or higher, and 4.5 or higher are preferred. Also, values ​​of 9.5 or lower, 9.0 or lower, 8.5 or lower, 8.0 or lower, 7.5 or lower, 7.0 or lower, 6.5 or lower, 6.0 or lower, 5.5 or lower, and 5.0 or lower are preferred. The upper and lower limits can be combined as appropriate. For example, W in copolymer B2 ２ / W Ｂ３２ The preferred values ​​are 2.8–9.5, 3.0–9.0, 3.5–8.5, 4.0–8.0, 4.0–6.0, and 4.0–5.0.

[0185] <Method for producing copolymers> Copolymer A can be produced, for example, by polymerizing monomer 1, monomer 2, and optionally one or both of monomer 3 and monomer 4. Copolymer B can be produced, for example, by polymerizing monomer 1, monomer 32, monomer 31, and optionally one or both of monomer 2 and monomer 4. Hereinafter, the monomers to be polymerized may be collectively referred to as "monomer 1, etc." The amount of monomer 1, etc. to be charged should be set appropriately to satisfy the desired copolymer composition.

[0186] (Initiators) It is preferable to use initiators when polymerizing copolymers. There are no particular restrictions on initiators, and they can be appropriately selected depending on the type of polymerizable reactive group such as monomer 1. Examples of initiators include organic peroxides, inorganic peroxides, azo compounds, etc., used in radical polymerization; organic acids, inorganic acids, Lewis acids, and thermal cationic polymerization initiators or photocatalytic cationic polymerization initiators used in cationic polymerization, etc.; and organometallic compounds and photoanionic polymerization initiators used in anionic polymerization, etc., that generate organic bases in the polymerization system. These may be used individually or in combination of two or more. There are no particular restrictions on organic peroxides, and examples include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, t-butyl hydroperoxide, t-butyl-α-cumyl peroxide, etc. These may be used individually or in combination of two or more. There are no particular restrictions on the inorganic peroxides, and 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 compounds, 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, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) may be used as azo polymerization initiators. There are no particular restrictions on organic acids, but examples include methanesulfonic acid. There are no particular restrictions on inorganic acids, but examples include hydrochloric acid, nitric acid, sulfuric acid, tetrafluoroboric acid, fluoroantimonic acid, hexafluorophosphate, etc. There are no particular restrictions on Lewis acids, but examples include trichloroaluminum, ethylaluminum dichloride, ethylaluminum sesquichloride, etc.There are no particular restrictions on the thermal cationic polymerization initiator; for example, benzyl(4-hydroxyphenyl)methylsulfonium hexafluoroantimonate is an example. There are no particular restrictions on the photocatalytic cationic polymerization initiator; for example, commercially available products such as WPI-113, WPI-116, and WPI-170 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) are examples. There are no particular restrictions on the organometallic compounds; for example, n-butyllithium, sec-butyllithium, t-butyllithium, diethylzinc, and triethylaluminum are examples. There are no particular restrictions on the photoanionic polymerization initiator; for example, commercially available products such as WPBG-266, WPBG-300, and WPGB-345 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) are examples.

[0187] The amount of polymerization 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 monomer 1, etc. 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.

[0188] (Molecular weight modifiers) When polymerizing monomer 1, etc., molecular weight modifiers may be used. Preferred molecular weight modifiers include aromatic compounds, mercapto alcohols, mercaptocarboxylic acids, and alkyl mercaptans, with mercaptocarboxylic acids or alkyl mercaptans being more preferred. Examples of molecular weight modifiers include mercaptoethanol, mercaptopropionic acid, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, stearyl mercaptan, and α-methylstyrene dimer (CH4). ２ = C(Ph)CH ２ C (CH ３ ) ２ Examples include pH, where pH is a phenyl group. The amount of molecular weight adjuster added is preferably 0 to 5 parts by mass, and more preferably 0 to 2 parts by mass, per 100 parts by mass of the total of monomer 1, etc.

[0189] (Chain Transfer Agent) When polymerizing monomer 1, etc., a chain transfer agent that enables living radical polymerization may be used for further molecular weight control. Examples of chain transfer agents include reversible addition-cleavage chain transfer agents, such as cyanomethyl dodecyltrithiocarbonate, 2-cyano-2-propylbenzodithioate, 2-(dodecylthiocarbonothiothio)-2-methylpropanoic acid, and methyl(phenyl)carbamodithioate cyanomethyl. In particular, when using monomers having two or more polymerizable groups in one molecule for polymerization, adding such a chain transfer agent is preferable because it can suppress gelation and precipitation of copolymer B. The amount of chain transfer agent to add 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 amount of monomer 1, etc.

[0190] (Catalyst) A catalyst may be used to obtain the copolymer. There are no particular restrictions on the catalyst, and examples include tin compounds such as dibutyltin dilaurate (dibutyltin dilaurate (DBTDL)); basic catalysts such as 1,4-diazabicyclo[2.2.2]octane (DABCO); and so on. 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 monomer 1, etc.

[0191] Polymerization methods include solution polymerization, emulsion polymerization, and bulk polymerization. Among these, solution polymerization and emulsion polymerization are preferred, with solution polymerization being particularly preferred. Solution polymerization is advantageous because it polymerizes monomer 1 etc. without using emulsifiers, making it easy to control the composition and less likely to introduce impurities.

[0192] Organic solvents are preferred as the medium used in solution polymerization. There are no particular restrictions on the organic solvent, and 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.

[0193] There are no particular restrictions on the hydrocarbon organic solvents, and examples include pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene. These may be used individually or in combination of two or more.

[0194] There are no particular restrictions on the alcohol-based organic solvents, and examples include ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol. These may be used individually or in combination of two or more.

[0195] There are no particular restrictions on the ketone-based organic solvents, and examples include methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone, and cyclohexanone. These may be used individually or in combination of two or more.

[0196] There are no particular restrictions on the ether-based organic solvents, and examples include diethyl ether, 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.

[0197] 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, glycerin triacetate, etc. These may be used individually or in combination of two or more.

[0198] In the emulsion polymerization method, for example, monomer 1 is polymerized in an emulsion containing monomer 1, an aqueous medium, an emulsifier, and a polymerization initiator. Examples of the aqueous medium include water or a mixed medium 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. The water-soluble organic solvent is preferably 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.

[0199] 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, the same emulsifiers as those described later can be used. As for emulsifiers, from the standpoint of excellent dispersion stability of the 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.

[0200] (Polymerization 1) When the polymerizable reactive group of monomer 1, etc. is a group having a polymerizable carbon-carbon double bond, a copolymer containing monomer 1, etc. can be obtained by polymerizing monomer 1, etc. 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.

[0201] (Polymerization 2) When the polymerizable reactive group of monomer 1 is a hydrolyzable group, a copolymer containing monomer 1 can be obtained by polymerizing monomer 1 in the presence of an initiator used in cationic polymerization or an initiator used in anionic polymerization. It is particularly 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. Furthermore, the initiator is not limited to organic acids, inorganic acids, and Lewis acids, but is not limited to any initiator that catalyzes hydrolysis; for example, inorganic bases and organic bases may be used. For example, when the hydrolyzable group is a hydrolyzable silyl group represented by formula 7 above, the hydrolyzable group is hydrolyzed and converted to a hydroxyl group, and the hydroxyl group undergoes dehydration condensation to generate a siloxane bond, and polymerization proceeds.

[0202] Polymerization 2 may be carried out by the sol-gel method (Method 1), or by coating an article with a solution containing monomer 1, etc., and then allowing polymerization to proceed using moisture in the air (Method 2).

[0203] In Method 1, it is preferable to add monomer 1 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.

[0204] In Method 2, a solution of monomer 1, etc., 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.

[0205] (Formation of salts in unit 32 or unit 31) When the copolymer has unit 3 (particularly unit 32 or unit 31), the cation donor group of unit 32 or the anion donor group of unit 31 may be partially or entirely ionized by a base or acid to form a salt. (The cation donor group and the anion donor group may be collectively referred to as the "ion donor group.") The above ionization may occur before or after polymerization. In other words, the ion donor group of monomer 32 or monomer 31 may be ionized before polymerization, or the ion donor group of unit 32 or unit 31 may be ionized after polymerization.

[0206] One example of a method for ionizing after polymerization is the following: First, monomer 1, monomer 3, and optionally one or both of monomers 2 and 4 are polymerized. Next, the resulting copolymer is mixed with a base or acid to obtain a copolymer in which some or all of the ion-donating groups of unit 3 are ionized.

[0207] One example of a method for ionizing before polymerization is the following: First, monomer 3 having an ion-donating group is mixed with a base or acid to obtain monomer 3 in which some or all of the ion-donating groups are ionized. Next, monomer 3 in which some or all of the ion-donating groups are ionized is polymerized with another monomer such as monomer 1 to obtain a copolymer in which some or all of the ion-donating groups of unit 3 are ionized.

[0208] Examples of bases include alkali metal hydroxides such as sodium hydroxide, alkaline earth metal hydroxides, amines such as monoethanolamine, and ammonia, with alkali metal hydroxides being preferred. Two or more bases may be used in combination. Examples of acids include the inorganic or organic acids mentioned above as salts of the cation donor group, and the preferred embodiments are similar. The oil-repellent composition of this disclosure preferably contains the above base or acid to the extent that the ion donor group is ionized. The extent to which the ion donor group is ionized depends on the type of monomer having the ion donor group, the base or acid, and their combination, but for example, it is 5 to 1,000 mol% relative to the ion donor group.

[0209] As for organic acids, when anionic acids are used as additives in paper treatment using external additives, or in environments where stability is required, such as under high pH conditions, acids with a pKa of 2.0 to 4.0 are preferred. Examples of organic acids with a pKa of 2.0 to 4.0 include lactic acid (pKa: 3.66), citric acid (pKa: 2.87), malic acid (pKa: 3.24), itaconic acid (pKa: 3.85), tartaric acid (pKa: 2.82), fumaric acid (pKa: 2.85), succinic acid (pKa: 4.00), and formic acid (pKa: 3.55). From the viewpoint of safety, water dispersibility, and the safety of chlorine polymers, lactic acid, citric acid, malic acid, and itaconic acid are preferred, with lactic acid and malic acid being more preferred.

[0210] For example, under low pH conditions of about 2.0 to 5.0, other organic acids with a pKa of less than 2.0 or a pKa of greater than 4.0 (more preferably organic acids with a pKa of 4.0 to 5.0) are also preferred. Other organic acids include acetic acid (pKa: 4.56), adipic acid (pKa: 4.26, 5.03), propionic acid (pKa: 4.67), oxalic acid (pKa: 1.04, 3.82), maleic acid (pKa: 1.75), and the like.

[0211] When using an organic acid, particularly a polycarboxylic acid, as the acid, the polycarboxylic acid is preferably of a molecular weight of 100 to 1,000,000. Examples of lower limits include 100, 150, 200, and 250. Examples of upper limits include 750,000, 500,000, 300,000, 100,000, 75,000, 50,000, 30,000, 10,000, 5,000, 3,000, 2,000, 1,000, 750, 500, and 300. The polycarboxylic acid is preferably of low molecular weight (for example, molecular weight of 1,000 or less). The inclusion of a polycarboxylic acid provides good oil resistance and can improve oil staining from folds. It can also suppress foaming during the application of the oil-resistant agent.

[0212] The lower limit of the amount of polycarboxylic acid per 100 parts by mass of copolymer B includes 10 parts by mass, 30 parts by mass, 60 parts by mass, 90 parts by mass, 120 parts by mass, 150 parts by mass, 180 parts by mass, 200 parts by mass, and 250 parts by mass. The upper limit of the above includes 2,000 parts by mass, 1,500 parts by mass, 1,000 parts by mass, 750 parts by mass, 500 parts by mass, 400 parts by mass, 300 parts by mass, 200 parts by mass, and 100 parts by mass.

[0213] Two or more bases or acids may be used in combination. The bases or acids can be appropriately selected depending on the ion-donating groups present in monomer 3 and unit 3.

[0214] (Unit formation after polymerization) The units contained in the copolymer 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, and then a compound Z2 having a reactive group (Z2 group) that can react with the reactive group (Z1 group) in unit Z1 of the precursor copolymer may be reacted with the reactive group (Z1 group) in unit Z1 to form each unit.

[0215] There are no particular restrictions on the reactive group (Z1 group), and examples include hydroxyl groups, amino groups, isocyanate groups, mercapto groups, acid anhydride groups, and acyl chloride groups.

[0216] Examples of reactive groups (Z2) include reactive groups that can react with the above-mentioned reactive group (Z1), such as isocyanate groups, hydroxyl groups, amino groups, acid anhydride groups, and acyl chloride groups.

[0217] For example, if the reactive group (Z1) of compound Z1 (unit Z1) is a hydroxyl group, and the reactive group of compound Z2 is an isocyanate group, the hydroxyl group of unit Z1 and the isocyanate group of compound Z2 react to form a urethane bond.

[0218] Compound Z2 is not particularly limited and examples include compounds having an isocyanate group, a hydroxyl group, an amino group, an acid anhydride group, or an acyl chloride group. These may be used individually or in combination of two or more.

[0219] There are no particular limitations on specific examples of compounds having an isocyanate group, and examples include benzyl isocyanate, 1-adamantyl isocyanate, cyclohexyl isocyanate, tert-butyl isocyanate, isopropyl isocyanate, ethyl isocyanate, butyl isocyanate, hexyl isocyanate, dodecyl isocyanate, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate. These may be used individually or in combination of two or more.

[0220] There are no particular limitations on specific examples of compounds having a hydroxyl group, and examples include ethanol, 1-butanol, 1-hexanol, 1-dodecanol, cyclohexanol, phenol, benzyl alcohol, 2-ethoxyethanol, 2-(2-ethoxyethoxy)ethanol, 2-methyl-1,3-propanediol, trimethylolethane, allyl alcohol, 3-butenol, 2-butenol, cis-2-penten-1-ol, trans-2-hexen-1-ol, propargyl alcohol, acetamidomethanol, and N-propionylethanolamine. These may be used individually or in combination of two or more.

[0221] There are no particular limitations on specific examples of compounds having an amino group, but examples include propylamine, butylamine, hexylamine, dodecylamine, cyclohexylamine, aniline, benzylamine, diethylamine, allylamine, N-allylmethylamine, propargylamine, and N-acetylethylenediamine. These may be used individually or in combination of two or more.

[0222] There are no particular limitations on specific examples of compounds having an acid anhydride group, and examples include acetic anhydride, propionic anhydride, butyric anhydride, decanoic anhydride, and benzoic anhydride. These may be used individually or in combination of two or more.

[0223] There are no particular limitations on specific examples of compounds having an acyl chloride group, and examples include acetyl chloride, propionyl chloride, butyrate chloride, decanoic acid chloride, and N-acetylglycinoyl chloride. These may be used individually or in combination of two or more.

[0224] There are no particular restrictions on the combination of the reactive group Z1 of compound Z1 and the reactive group Z2 of compound Z2, but for example, the following combinations are preferred: Combination 1: Z1 is a hydroxyl group and Z2 is an isocyanate group. Combination 2: Z1 is an isocyanate group and Z2 is a hydroxyl group. Combination 3: Z1 is an acid anhydride group or an acyl chloride group and Z2 is an amino group. Combination 4: Z1 is an amino group and Z2 is an acid anhydride group or an acyl chloride group. Combination 5: Z1 is an amino group and Z2 is an isocyanate group. Combination 6: Z1 is an isocyanate group and Z2 is an amino group. Combinations 1 and 2 result in a urethane bond, combinations 3 and 4 result in an amide bond, and combinations 5 and 6 result in a urea bond. Among these, combinations 1 and 2 are particularly preferred.

[0225] <Liquid Media> Examples of liquid media include non-aqueous media and aqueous media. When the liquid media is a non-aqueous media, the oil-repellent composition is preferably a polymer solution containing a copolymer and a non-aqueous media, 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. When the liquid media is an aqueous media, the oil-repellent composition is preferably an aqueous dispersion containing a copolymer and an aqueous media, in which the copolymer is dispersed in the aqueous media.

[0226] (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 or disperse the copolymer, and examples include solvents similar to the solvents described above as media used in solution polymerization, water-soluble organic solvents described later, and amide-based organic solvents.

[0227] There are no particular restrictions on the amide-based organic solvent; examples include dimethylacetamide, 3-methoxydimethylpropanamide, 3-butoxydimethylpropanamide, and methylpyrrolidone. These may be used individually or in combination of two or more. Two or more non-aqueous media may also be used.

[0228] For example, when the substrate to be treated with the oil-repellent composition is a porous body as described later, the oil-repellent composition preferably contains a polymer solution comprising a copolymer and a non-aqueous medium. A water-soluble organic solvent is preferred as the non-aqueous medium. Furthermore, it is preferable that the amount of emulsifier be 0.1 parts by mass or less per 100 parts by mass of copolymer, and it is also preferable that the composition contains no emulsifier at all.

[0229] (Aqueous medium) Examples of aqueous medium 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 the copolymer 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. 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.

[0230] For example, when the substrate to be treated with the oil-repellent composition is paper as described later, the oil-repellent composition preferably contains an aqueous dispersion containing a copolymer and an aqueous medium. Water is preferred as the aqueous medium, and it is preferable that the water content is 80% by mass or more relative to the total mass of the aqueous medium. Furthermore, it is preferable that the emulsifier is 0.1 parts by mass or less per 100 parts by mass of copolymer, and it is also preferable that the emulsifier is not present at all.

[0231] <Other Components> Examples of other components include emulsifiers (anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, etc.), resins other than copolymers in this disclosure (acrylic resins, urethane resins, silicone resins, etc.), adhesives, crosslinking agents, catalysts, organic fillers, inorganic fillers, supporters, retainers, flocculants, buffering agents, disinfectants, biocides, metal ion sequestering agents, hydrophobic agents, surfactants, defoamers, and volatile organic solvents. Furthermore, examples of concomitant agents for external additive processes described later include paper strength enhancers (various starches, resins, etc.), sizing agents, penetrating agents, defoamers, chelating agents, dyes, pigments, binders, acids, alkalis, alginates, and aluminum sulfates. Examples of concomitant agents for internal additive processes described later include coagulants, yield enhancers, sizing agents, paper strength enhancers, pigments, dyes, and pH adjusters. The examples of other components are not limited to these. Two or more types of other components may be used.

[0232] When an oil-repellent composition contains a crosslinking agent, adhesion to articles tends to improve. Preferred 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. 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 a hydrophilic group.

[0233] 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.

[0234] Carbodiimide 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 crosslinking agents are polymers having oxazoline groups in their molecules and exhibit excellent reactivity with carboxyl groups on the surface of articles.

[0235] Other crosslinking agents include, for example, 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.

[0236] When an 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. Preferred catalysts include, for example, inorganic amine salts and organic amine salts. An example of an inorganic amine salt is ammonium chloride. An example of an organic amine salt is amino alcohol hydrochloride and semicarbazide hydrochloride. An example of an amino alcohol hydrochloride is monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanolamine hydrochloride, and 2-amino-2-methylpropanol hydrochloride.

[0237] <Proportion of each component> The copolymer content is preferably 1 to 99% by mass, more preferably 55 to 95% by mass, even more preferably 60 to 90% by mass, and particularly preferably 65 to 85% by mass, based on the total solid content of the oil-repellent composition.

[0238] When the oil-repellent composition contains a liquid medium, the amount of the liquid medium can be appropriately selected according to the desired solid content concentration of the oil-repellent composition. The solid content concentration of the oil-repellent composition immediately after manufacture is preferably 5 to 80% by mass, more preferably 10 to 50% by mass, and even more preferably 10 to 40% by mass. When the oil-repellent composition is used for coating articles, the solid content concentration of the 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.

[0239] When the oil-repellent composition is used for coating articles, the copolymer content is preferably 0.01 to 20% by mass relative to the total mass of the oil-repellent composition. In particular, when the substrate to be treated is paper or a porous substrate, the copolymer content in the oil-repellent composition is more preferably 0.01 to 10% by mass, even more preferably 0.1 to 5% by mass, and may be 0.1 to 1% by mass. According to the oil-repellent composition of this embodiment, it is considered that high oil repellency can be exhibited even at low copolymer concentrations.

[0240] When the oil-repellent composition is an aqueous dispersion with a solid content concentration of about 15 to 20% by mass (more preferably an aqueous dispersion with a solid content concentration of 15% by mass), the viscosity of the oil-repellent composition is preferably 300 mPa·s or less, more preferably 200 mPa·s or less, even more preferably 100 mPa·s or less, even more preferably 50 mPa·s or less, particularly preferably 31 mPa·s or less, and most preferably 20 mPa·s or less, from the viewpoint of workability.

[0241] The oil-repellent composition is preferably a non-fluorine-based oil-repellent composition. In other words, the fluorine atom content relative to the total mass of the 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, particularly preferably 0.1% by mass or less, and most preferably no fluorine atoms at all. The fluorine atom content relative to the total mass of the oil-repellent composition can be measured by methods such as combustion ion chromatography.

[0242] In the oil-repellent composition containing copolymer A, since copolymer A contains unit 1 and unit 2, excellent oil repellency can be imparted to the substrate. Articles treated with the oil-repellent composition of this embodiment exhibit excellent oil repellency. They also have good water resistance and air permeability. Furthermore, depending on the application of the article, oil resistance to high temperatures (e.g., 60°C or higher, more strictly 80°C or higher, and even more strictly 100°C or higher) may be required, and the oil-repellent composition of this embodiment can also impart high-temperature oil resistance. In the oil-repellent composition of this embodiment, it is believed that the oil-repellent effect is exerted by the trialkylsilyl group of unit 1. Furthermore, by including unit 2 as well, the dissolution of copolymer A in oil and swelling due to oil are suppressed, and the oil-repellent effect of the trialkylsilyl group is thought to be maximized.

[0243] In the oil-repellent composition containing copolymer B, since copolymer B contains units 1, 32, and 31, excellent oil repellency can be imparted to the substrate. Articles treated with the oil-repellent composition of this embodiment exhibit excellent oil repellency. They also have good water resistance and air permeability. Furthermore, depending on the application of the article, oil resistance to high temperatures (e.g., 60°C or higher, more strictly 80°C or higher, and even more strictly 100°C or higher) may be required, and the oil-repellent composition of this embodiment can also impart high-temperature oil resistance. In the oil-repellent composition of this embodiment, it is believed that the oil-repellent effect is exerted by the trialkylsilyl group of unit 1. In addition, by including unit 32 having a cation donor group, unit 31 having an anion donor group, and unit 2 in addition to unit 1, ionization is possible under both acidic and basic conditions, thus improving pH stability, and it is believed that intermolecular ionic crosslinking becomes possible, improving fixation to the substrate.

[0244] <Applications> The oil-repellent composition of this embodiment is suitably used to impart liquid repellency to materials such as fibers, glass, paper, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded products, and porous materials (porous resins, porous fibrous materials, etc.). From the viewpoint of oil repellency, the oil-repellent composition of this embodiment is preferably for paper or porous materials, and more preferably for paper. The liquid-repellent composition of this embodiment can be used, for example, as a water-repellent agent, oil-repellent agent, water-repellent and oil-repellent agent, water-resistant agent, oil-resistant agent, water-resistant and oil-resistant agent, antifouling agent, and oleophobic agent. Furthermore, the liquid-repellent composition of this embodiment can also be used as a moisture-proofing agent, water-slip agent, mold release agent, release agent, resin adhesion inhibitor, and biological adhesion inhibitor.

[0245] ≪Articles≫ An article according to one embodiment of the present disclosure is an article treated with an oil-repellent composition. The article may include any of the following base materials, and at least a portion of the base material may be treated with the oil-repellent composition of this embodiment. Examples of base materials (articles to be treated) to be treated with the oil-repellent composition include fibers, textile fabrics (woven textiles, knitted textiles, nonwoven fabrics, napped fabrics, etc.), textile products made of 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, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded products, and porous materials (porous resins, porous fibrous materials, etc.). As the porous material, porous resins are preferred. Porous resins are used, for example, as filters (filter media). Examples of porous resin materials include polypropylene, polyethylene terephthalate, and polytetrafluoroethylene. Examples of materials for porous fibrous bodies include glass fibers, cellulose nanofibers, carbon fibers, and cellulose acetate fibers. The oil-repellent composition of this embodiment can impart oil repellency to an article while ensuring breathability. Therefore, the base material is preferably one that requires oil repellency and breathability, or a constituent material thereof, such as paper, a porous body, or fibers, with paper or a porous body being preferred, and paper being more preferred.

[0246] The types of fibers are not particularly limited, but include natural fibers such as cotton, wool, silk, or cellulose; chemical fibers such as polyester, polyamide, acrylic, aramid, rayon, or lyocell; and fibers obtained using multiple of these fibers. Fibers used 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 typically between 10 μm and 5 cm.

[0247] The method for processing an article is simply to allow the oil-repellent composition to adhere to the article to be processed. For example, if the oil-repellent composition contains a liquid medium, the article can be processed with the oil-repellent composition by known methods such as coating, impregnation, immersion, spraying, brushing, padding, sizing press, or rolling, and then dried. The amount of solids in the oil-repellent composition to be adhered to the article to be processed is not particularly limited and can be set appropriately depending on the type and use of the article to be processed. For example, 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 copolymer content in the oil-repellent composition to be adhered to the article to be processed is not particularly limited and can be set appropriately depending on the type and use of the article to be processed. For example, 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 carried out at room temperature or by heating, and heating is preferred. When heating, the heating temperature is preferably 90 to 200°C. Furthermore, if the oil-repellent composition contains a crosslinking agent, it is preferable to heat it to a temperature above the crosslinking temperature of the crosslinking agent for curing, if necessary.

[0248] <Oil-resistant paper> The article of this embodiment may be oil-resistant paper in which pulp or paper has been treated with an oil-repellent composition, and oil-resistant paper is preferred. Methods for manufacturing oil-resistant paper include applying or impregnating a paper substrate with an oil-repellent composition (external addition method) and making paper from a pulp slurry containing an oil-repellent composition (internal addition method). In the external addition method and the internal addition method, the oil-repellent composition may be used after being diluted with water or an aqueous medium. The solid content concentration of the oil-repellent composition used in the method for manufacturing oil-resistant paper is preferably 10 to 30% by mass, and more preferably 20 to 25% by mass.

[0249] (External Additive Processing) As a paper base material, one type of pulp slurry, in which pulp is dispersed in water, is used alone, or two or more types are mixed in any ratio, beaten, chemicals are added, and then the paper is formed using a wire. Examples of forms include continuous, long web-like forms, sheet-like forms obtained by cutting the web, and molded bodies (containers, etc.) obtained by a pulp molding machine. The basis weight is, for example, 10 to 500 g / m². ２ But that's fine.

[0250] Specific examples of pulp raw materials include wood such as coniferous and deciduous trees; herbaceous plants such as bagasse, rice straw, bamboo, reeds, and coconut husks; and recycled paper. Of the pulp raw materials, pulp made from wood and herbaceous plants is called fresh pulp, and pulp made from recycled paper is called recycled pulp. Fresh pulp is called by different names depending on the manufacturing method. Examples of fresh pulp names include kraft pulp (KP), sulfite pulp (SP), soda pulp, mechanical pulp (MP), thermomechanical pulp (TMP), and chemothermetic pulp (CTMP). Fresh pulp may be made by performing one or more bleaching treatments as needed. Recycled pulp may be made by performing one of the following processes as needed: disintegration, dust removal, deinking, and bleaching, or by combining multiple processes.

[0251] The paper substrate may contain sizing agents, fixing agents, dry strength agents, wet strength agents, aluminum sulfate, yield enhancers, dyes, pigments, fillers, etc., to the extent that it does not impair the effects of the present invention.

[0252] The oil-repellent composition may contain concomitant agents. Examples of concomitant agents used in external additive processing include paper strength enhancers (various starches, resins, etc.), sizing agents, penetrating agents, defoaming agents, chelating agents, dyes, pigments, binders, acids, alkalis, alginates, and aluminum sulfates.

[0253] Preferred paper strength enhancers include, for example, starch and resins. Paper strength enhancers contribute to strengthening bonds between pulps, for example, by forming hydrogen bonds with copolymers, and are therefore thought to contribute to improving the water resistance and wet strength of paper treated with an oil-repellent composition. Examples of starches include hydroxyethylated starch, hydroxyethyl etherified starch, cationized starch, amphoteric starch, oxidized starch, phosphorylated starch, phosphate esterified starch, enzyme-modified starch, and raw starch, with hydroxyethylated starch being preferred. Examples of resins include polyamide epichlorohydrin resin, polyamine epichlorohydrin resin, polyamideamine epichlorohydrin resin, polyvinyl alcohol resin, and polyacrylamide resin, with polyvinyl alcohol resin being preferred.

[0254] The application or impregnation of the oil-repellent composition may be carried out at any stage after papermaking, including the sizing press stage after papermaking, wet pressing, and pre-drying, or the stage using a coater after the sizing press. A coating machine may be used to apply the oil-repellent composition. Examples of coating machines include sizing presses, coaters, and printing presses. Examples of sizing presses include two-roll sizing presses, film transfer sizing presses, and calender sizing presses. Examples of coaters include roll coaters, air knife coaters, die coaters, blade coaters, bar coaters, bill blade coaters, and short dwell blade coaters. Examples of printing presses include gravure printing presses, flexographic printing presses, and offset printing presses.

[0255] After applying or impregnating the paper substrate with the oil-repellent composition, the paper substrate is dried. The drying method may be by heat drying or by air drying without heat. The drying temperature is preferably 20 to 300°C, and more preferably 20 to 250°C.

[0256] (Internal Addition Process) The pulp slurry contains water and pulp dispersed in water. The raw materials for the pulp are the same as those described for the external addition process above. The pulp slurry may be produced by dissociating dry pulp in a dissociator, or by diluting wet pulp produced in a pulp manufacturing facility. One type of pulp slurry may be used alone, or two or more types may be mixed in any proportion. The concentration of pulp in the pulp slurry is preferably 0.1 to 10% by mass.

[0257] The oil-repellent composition may be added at any stage before the pulp slurry is supplied onto the wires of the paper machine. Concomitant agents may also be added to the pulp slurry. Examples of concomitant agents used in the internal additive process include coagulants, yield enhancers, sizing agents, paper strength enhancers, pigments, dyes, and pH adjusters.

[0258] A paper machine can be used to make paper from pulp slurry. The paper machine can be any device capable of dewatering the pulp slurry on a wire. The paper machine can be a continuous paper machine such as a wire mesh paper machine, or a batch-type pulp molding machine. A batch-type pulp molding machine is, for example, a device that dewaters pulp slurry using a molding frame made of wire to produce a molded product.

[0259] A preferred embodiment of the present invention is as follows: [C1] An oil-repellent composition comprising the following copolymer A and an aqueous medium. Copolymer A: A copolymer comprising a unit based on a monomer represented by the following formula 1, a unit based on a nonionic monomer having a solubility in water at 20°C of 1 g / 100 mL or more, and a unit based on an ionic monomer having a cation-donating group. X １ -A １ -B １ ... (Equation 1) In Equation 1 above, X １ A is a monovalent polymerizable reactive group, １ is a divalent organic group, B １ This is a monovalent organic group represented by formula 3 below or a monovalent organic group represented by formula 4 below. Ａ１＊ -Si(OSiR) １５ ３ ) ３－ｂ R１６ ｂ ... (Equation 3) In Equation 3 above, R 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, R 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 independently a linear or branched alkyl group having 1 to 6 carbon atoms, and R １６ Each of these is independently a linear or branched alkyl group having 1 to 6 carbon atoms, b is an integer from 0 to 2, and c is an integer from 0 to 2. Ａ１＊ - is A １ This is a combination of the two. Ａ１＊ -SiR １７ ２ (OSiR １８ ２ ) ｎ OSiR １９ ３ ... (Equation 4) In Equation 4 above, R １７ , R １８ and R １９ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms, and n is an integer from 0 to 10. Ａ１＊ - is A １ This is a bonding relationship. [C2] An oil-repellent composition of [C1] wherein the content of units based on the nonionic monomer is more than 20% by mass relative to the total units constituting the copolymer A. [C3] An oil-repellent composition of [C1] or [C2] wherein the nonionic monomer does not have a polyoxyalkylene chain, and the content of units based on the nonionic monomer is more than 10% by mass relative to the total units constituting the copolymer A. [C4] The content ratio (mol%) of units based on the monomer represented by formula 1 relative to the total units constituting the copolymer A is M Ａ１The content percentage (mol%) of the unit based on the above nonionic monomer is M Ａ２ When that happens, M Ａ２ / M Ａ１ An oil-repellent composition of any of [C1] to [C3], wherein the ratio is 1.2 to 5.2. [C5] The above M Ａ２ / M Ａ１ An oil-repellent composition of any of [C1] to [C4], wherein the amount is 4.0 to 5.0. [C6] An oil-repellent composition of any of [C1] to [C5], wherein the content of units based on the monomer represented by the above formula 1 is more than 25% by mass relative to the total units constituting the copolymer A. [C7] X in the above formula 1 １ However, the oil-repellent composition is any of [C1] to [C6], which is a group having a polymerizable carbon-carbon double bond. [C8] R in formula 4 above １９The oil-repellent composition is any of [C1] to [C7], wherein the alkyl group having 1 to 3 carbon atoms. [C9] The oil-repellent composition is any of [C1] to [C8], wherein the molecular weight of the monomer represented by the above formula 1 is less than 500. [C10] The oil-repellent composition is any of [C1] to [C9], wherein the content of units based on the above nonionic monomer is 40% by mass or more relative to the total units constituting the copolymer A, and the content of units based on the above ionic monomer is 15% by mass or less relative to the total units constituting the copolymer A. [C11] The oil-repellent composition is any of [C1] to [C10], wherein the content of units based on the above nonionic monomer is 50 to 60% by mass relative to the total units constituting the copolymer A, and the content of units based on the above ionic monomer is 7 to 12% by mass relative to the total units constituting the copolymer A. [C12] An oil-repellent composition from any of [C1] to [C11] in which the ionic monomer having the cation-donating group has a heterocycle. [C13] An oil-repellent composition from any of [C1] to [C12] further comprising polyvinyl alcohol. [C14] An oil-repellent composition from any of [C1] to [C13] in which the copolymer A does not contain units based on an ionic monomer having an anion-donating group. [C15] An oil-repellent composition from any of [C1] to [C14] further comprising an acid, wherein at least a portion of the cation-donating group is ionized by the acid. [C16] An oil-repellent composition from any of [C1] to [C15] in which the pKa of the acid is greater than 4.0. [C17] An oil-repellent composition from any of [C1] to [C16] in which the pH at 25°C is less than 7.0.

[0260] A preferred embodiment of the present invention is as follows: [D1] An oil-repellent composition comprising the following copolymer A and an aqueous medium. Copolymer A: A copolymer comprising a unit based on a monomer represented by the following formula 1, a unit based on a nonionic monomer having a solubility in water of 1 g / 100 mL or more at 20°C, and a unit based on an ionic monomer having an anion donor group. X １ -A １ -B １ ... (Equation 1) In Equation 1 above, X １ A is a monovalent polymerizable reactive group, １ is a divalent organic group, B１ This is a monovalent organic group represented by formula 3 below or a monovalent organic group represented by formula 4 below. Ａ１＊ -Si(OSiR) １５ ３ ) ３－ｂ R １６ ｂ ... (Equation 3) In Equation 3 above, R 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, R 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 independently a linear or branched alkyl group having 1 to 6 carbon atoms, and R １６ Each of these is independently a linear or branched alkyl group having 1 to 6 carbon atoms, b is an integer from 0 to 2, and c is an integer from 0 to 2. Ａ１＊ - is A １ This is a combination of the two. Ａ１＊ -SiR １７ ２ (OSiR １８ ２ ) ｎ OSiR １９ ３ ... (Equation 4) In Equation 4 above, R １７ , R １８ and R １９ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms, and n is an integer from 0 to 10. Ａ１＊ - is A １This is a bonding relationship. [D2] The oil-repellent composition of [D1] wherein the content of units based on the nonionic monomer is more than 40% by mass relative to the total units constituting copolymer A, and the nonionic monomer does not have a polyoxyalkylene chain. [D3] The content ratio (mol%) of units based on the monomer represented by formula 1 relative to the total units constituting copolymer A is M Ａ１ The content percentage (mol%) of the unit based on the above nonionic monomer is M Ａ２ When that happens, M Ａ２ / M Ａ１ An oil-repellent composition of [D1] or [D2] wherein the ratio is 2.3 or higher. [D4] The above M Ａ２ / M Ａ１ A oleophobic composition of any of [D1] to [D3], wherein the ratio is 5.3 or less. [D5] The above M Ａ２ / M Ａ１ An oil-repellent composition of any of [D1] to [D4], wherein the ratio is 4.0 to 5.0. [D6] The content ratio (mol%) of units based on the nonionic monomer relative to the total units constituting the copolymer A is M Ａ２ The content percentage (mol%) of the unit based on the above anionic monomer is M Ａ３１ When that happens, M Ａ２ / M Ａ３１ A oleophobic composition of any of [D1] to [D5], wherein the ratio is 3.5 or higher. [D7] The above M Ａ２ / M Ａ３１ An oil-repellent composition of any of [D1] to [D6], wherein X is 7.0 to 10.0. [D8] An oil-repellent composition of any of [D1] to [D7], wherein the content of units based on the monomer represented by the above formula 1 is more than 25% by mass relative to the total units constituting the copolymer A. [D9] X in the above formula 1 １ However, the oil-repellent composition is one of [D1] to [D8], which is a group having a polymerizable carbon-carbon double bond. [D10] R in the above formula 4 １９The oil-repellent composition is any of [D1] to [D9], wherein the alkyl group has 1 to 3 carbon atoms. [D11] The oil-repellent composition is any of [D1] to [D10], wherein the molecular weight of the monomer represented by the above formula 1 is less than 500. [D12] The oil-repellent composition is any of [D1] to [D11], wherein the content of units based on the above nonionic monomer is 50 to 60% by mass relative to the total units constituting the copolymer A, and the content of units based on the above ionic monomer is 1 to 6% by mass relative to the total units constituting the copolymer A. [D13] The oil-repellent composition is any of [D1] to [D12], further comprising polyvinyl alcohol. [D14] The oil-repellent composition is any of [D1] to [D13], wherein the copolymer A does not contain units based on an ionic monomer having a cation donor group. [D15] Any oil-repellent composition from [D1] to [D14], further comprising a base, wherein at least a portion of the anion-donating group is ionized by the base. [D16] Any oil-repellent composition from [D1] to [D15], wherein the base is an alkali metal hydroxide, an alkaline earth metal hydroxide, an amine, or ammonia. [D17] Any oil-repellent composition from [D1] to [D16], wherein the pH at 25°C is greater than 7.0.

[0261] A preferred embodiment of the present invention is as follows: [E1] An oil-repellent composition comprising the following copolymer B. Copolymer B: A copolymer comprising a unit based on a monomer represented by the following formula 1, a unit based on a nonionic monomer having a solubility in water of 1 g / 100 mL or more at 20°C, a unit based on an ionic monomer having a cation-donating group, and a unit based on an ionic monomer having an anion-donating group. X １ -A １ -B １ ... (Equation 1) In Equation 1 above, X １ A is a monovalent polymerizable reactive group, １ is a divalent organic group, B １ This is a monovalent organic group represented by formula 3 below or a monovalent organic group represented by formula 4 below. Ａ１＊ -Si(OSiR) １５ ３ ) ３－ｂ R １６ ｂ... (Equation 3) In Equation 3 above, R 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, R 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 independently a linear or branched alkyl group having 1 to 6 carbon atoms, and R １６ Each of these is independently a linear or branched alkyl group having 1 to 6 carbon atoms, b is an integer from 0 to 2, and c is an integer from 0 to 2. Ａ１＊ - is A １ This is a combination of the two. Ａ１＊ -SiR １７ ２ (OSiR １８ ２ ) ｎ OSiR １９ ３ ... (Equation 4) In Equation 4 above, R １７ , R １８ and R １９ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms, and n is an integer from 0 to 10. Ａ１＊ - is A １ This is a bonding relationship. [E2] The oil-repellent composition of [E1], wherein the content of units based on the above nonionic monomer is more than 20% by mass relative to the total units constituting the copolymer B. [E3] The oil-repellent composition of [E1] or [E2], wherein the above nonionic monomer does not have a polyoxyalkylene chain. [E4] The oil-repellent composition of any of [E1] to [E3], wherein the content of units based on the monomer represented by the above formula 1 is more than 25% by mass relative to the total units constituting the copolymer B. [E5] X in the above formula 1 １However, the oil-repellent composition is any of [E1] to [E4], which is a group having a polymerizable carbon-carbon double bond. [E6] R in formula 4 above １９ However, an oil-repellent composition which is an alkyl group having 1 to 3 carbon atoms, one of [E1] to [E5]. [E7] An oil-repellent composition which is one of [E1] to [E6] in which the molecular weight of the monomer represented by the above formula 1 is less than 500. [E8] The content ratio (mass%) of units based on the monomer having the above anion-donating group relative to the total units constituting the copolymer B is W Ｂ３１ The content ratio (mass%) of units based on the monomer having the above cation donor group is W Ｂ３２ When that happens, W Ｂ３２ / W Ｂ３１ An oil-repellent composition of any of [E1] to [E7] wherein the ratio is greater than 2.0. [E9] The above W Ｂ３２ / W Ｂ３１ An oil-repellent composition of [E8] in which is 6.0 to 7.0 or less. [E10] The content ratio (mass%) of units based on the nonionic monomer to the total units constituting the copolymer B is W Ｂ２ The content ratio (mass%) of the unit based on the cationic monomer is W Ｂ３２ When that happens, W Ｂ２ / W Ｂ３２ An oil-repellent composition of any of [E1] to [E9], wherein the ratio is 2.8 to 9.5. [E11] The above W Ｂ２ / W Ｂ３２[E10] An oil-repellent composition having a pKa of 4.0 to 5.0 or less. [E12] An oil-repellent composition of any of [E1] to [E11], wherein the content of units based on the nonionic monomer is 40 to 60% by mass relative to the total units constituting the copolymer B, the content of units based on the cationic monomer is 7.5 to 12.5% ​​by mass relative to the total units constituting the copolymer B, and the content of units based on the anionic monomer is 0.5 to 5.0% by mass relative to the total units constituting the copolymer B. [E13] An oil-repellent composition of any of [E1] to [E12], further comprising an acid, wherein at least a portion of the cation-donating group is ionized by the acid. [E14] An oil-repellent composition of any of [E1] to [E13], wherein the pKa of the acid is greater than 4.0. [E15] An oil-repellent composition of any of [E1] to [E14], wherein the pH at 25°C is less than 7.0. [E16] The percentage (by mass) of units based on the monomer having the anion donor relative to the total units constituting copolymer B is W Ｂ３１ The content ratio (mass%) of units based on the monomer having the above cation donor group is W Ｂ３２ When that happens, W Ｂ３２ / W Ｂ３１ An oil-repellent composition of any of [E1] to [E7] wherein W is greater than 0 and less than or equal to 2.0. [E17] The above W Ｂ３２ / W Ｂ３１ An oil-repellent composition of [E16] in which is greater than 0 and less than 1.0. [E18] The above W Ｂ３２ / W Ｂ３１An oil-repellent composition of [E17], wherein the amount is 0.1 to 0.4. An oil-repellent composition of any of [E1] to [E7] and [E16] to [E18], wherein the content of units based on the nonionic monomer is 50 to 60% by mass relative to the total units constituting the copolymer B, the content of units based on the cationic monomer is 0.5 to 2.0% by mass relative to the total units constituting the copolymer B, and the content of units based on the anionic monomer is 3.0 to 5.0% by mass relative to the total units constituting the copolymer B. An oil-repellent composition of any of [E1] to [E7] and [E16] to [E19], further comprising a base, wherein at least a portion of the anion-donating group is ionized by the base. [E21] Any oil-repellent composition from [E1] to [E7] and [E16] to [E20], wherein the base is an alkali metal hydroxide, an alkaline earth metal hydroxide, an amine, or ammonia. [E22] Any oil-repellent composition from [E1] to [E7] and [E16] to [E21], wherein the pH at 25°C is greater than 7.0. [E23] Any oil-repellent composition from [E1] to [E22], wherein the ionic monomer having the cation-donating group has a heterocycle. [E24] Any oil-repellent composition from [E1] to [E23], further comprising polyvinyl alcohol.

[0262] A preferred embodiment of the present invention is as follows: [F1] An oil-repellent composition for porous materials comprising the following copolymer. Copolymer: A copolymer comprising a unit based on a monomer represented by the following formula 1, a unit based on a nonionic monomer having a solubility in water at 20°C of 1 g / 100 mL or more, and a unit based on an ionic monomer. X １ -A １ -B １ ... (Equation 1) In Equation 1 above, X １ A is a monovalent polymerizable reactive group, １ is a divalent organic group, B １ This is a monovalent organic group represented by formula 3 below or a monovalent organic group represented by formula 4 below. Ａ１＊ -Si(OSiR) １５ ３ ) ３－ｂ R １６ ｂ... (Equation 3) In Equation 3 above, R 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, R 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 independently a linear or branched alkyl group having 1 to 6 carbon atoms, and R １６ Each of these is independently a linear or branched alkyl group having 1 to 6 carbon atoms, b is an integer from 0 to 2, and c is an integer from 0 to 2. Ａ１＊ - is A １ This is a combination of the two. Ａ１＊ -SiR １７ ２ (OSiR １８ ２ ) ｎ OSiR １９ ３ ... (Equation 4) In Equation 4 above, R １７ , R １８ and R １９ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms, and n is an integer from 0 to 10. Ａ１＊ - is A １This is a bonding relationship. [F2] An oil-repellent composition of [F1] in which the units based on the above ionic monomer include units based on an ionic monomer having a cation donor group and units based on an ionic monomer having an anion donor group. [F3] An oil-repellent composition of [F1] or [F2] in which the content of the units based on the above nonionic monomer is more than 20% by mass relative to the total units constituting the copolymer. [F4] An oil-repellent composition of any of [F1] to [F3] in which the above nonionic monomer does not have a polyoxyalkylene chain. [F5] An oil-repellent composition of any of [F1] to [F4] in which the content of the units based on the monomer represented by the above formula 1 is more than 25% by mass relative to the total units constituting the copolymer. [F6] X in the above formula 1 １ However, the oil-repellent composition is one of [F1] to [F5], which is a group having a polymerizable carbon-carbon double bond. [F7] R in the above formula 4 １９ [F1] to [F6] any oil-repellent composition, wherein the polymer is an alkyl group having 1 to 3 carbon atoms. [F8] Any oil-repellent composition, wherein the monomer represented by formula 1 has a molecular weight of less than 500. [F9] Any oil-repellent composition, wherein the porous body is a porous resin. [F10] Any oil-repellent composition, wherein the porous resin is at least one selected from the group consisting of polypropylene, polyethylene terephthalate, and polytetrafluoroethylene. [F11] Any oil-repellent composition, wherein the porous resin is at least one selected from the group consisting of polypropylene, polyethylene terephthalate, and polytetrafluoroethylene. [F12] Any oil-repellent composition, wherein the porous body is a filter. [F13] Any oil-repellent composition, wherein the porous body is further a non-aqueous medium. [F14] An oil-repellent composition of any of [F1] to [F13] that does not contain water or contains 1% by mass or less water.

[0263] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, room temperature is 25°C. Unless otherwise specified, "%" means "mass%". Examples 1 to 15 and Examples 18 to 84 are examples, and Examples 16 to 17 and Examples 85 to 86 are comparative examples.

[0264] <Evaluation Method> (Unit Content) The composition ratio of the (co)polymer (the ratio of each unit to the total number of units constituting the (co)polymer) was determined by adding 1,4-bis(trifluoromethyl)benzene as a standard substance and immersing it in deuterated chloroform. １ By measuring 1H NMR and comparing the integral ratios, the results were calculated and confirmed to be in close agreement with the proportion of each monomer used.

[0265] (Measurement of Weight-Average Molecular Weight (Mw)) Gel permeation chromatography (GPC) spectra of several monodisperse polymethyl methacrylate (PMMA) samples with different degrees of polymerization, commercially available as standard samples for molecular weight measurement, were measured using a commercially available GPC measuring device (Tosoh Corporation, device name: HLC-8320GPC) with a differential refraction detector. A calibration curve was created based on the relationship between the molecular weight of PMMA and its retention time. A solution containing the copolymer obtained by polymerization, with a solid content concentration of 20% by mass, was diluted with N,N-dimethylformamide to a solid content concentration of 0.5% by mass. After passing the solution through a 0.5 μm filter, the GPC spectrum of the sample was measured using the GPC measuring device with a differential refraction detector. The weight-average molecular weight (Mw) of the sample was determined by computer analysis of the GPC spectrum of the sample using the above calibration curve. The results are shown in the table.

[0266] (Solubility in water) The monomer was added to 100 mL of water and shaken vigorously for 30 seconds every 5 minutes at 20°C. The amount (g) that dissolved within 30 minutes was defined as the solubility of the monomer in water.

[0267] (pH) The pH of the compositions obtained in each example was measured at 25°C using a pH meter (Fisher Scientific, Fisherbrand® Accumet® Basic AB315).

[0268] (Viscosity) The viscosity of the compositions (aqueous dispersions) with a solid content of approximately 15% after ionization and desolvation, obtained in each example, was measured at 25°C and 100 rpm using a viscometer (Brookfield DV-II+Pro, manufactured by BROOKFIELD ENGINEERING LABORATORIES). The unit of viscosity in the table is [mPa·S].

[0269] (Weight-based oil resistance: 60°C corn oil) The test paper was placed on a frosted glass slab. Two 0.75-inch diameter cotton flannel discs were placed in the center of the test paper, and a 50g weight was placed on the flannel discs. The oven was preheated to 60°C for 30 minutes. The weight was then removed, and six drops of corn oil were dropped onto the flannel discs in the oven. The weight was then returned to the oil drop locations. The oven was maintained at 60°C for another hour. After that, the test paper was removed from the oven, and the weight, flannel discs, and test paper were lifted from the frosted glass slab. The condition of the frosted glass slab was visually observed and evaluated according to the following criteria: A: The frosted glass slab is not wet at the oil drop locations. B: A portion of the frosted glass slab (less than 40% of the drop area) is wet at the oil drop locations. C: At the point where the oil was dropped, most of the frosted glass fragment (more than 40% of the area where the oil was dropped) was wet. D: The frosted glass fragment was wetter than the point where the oil was dropped.

[0270] (Heat-resistant water) 0.5 mL of deionized water heated to 80°C was dropped onto the test paper. After standing for 5 minutes, the degree of penetration of the deionized water into the test paper was visually observed and evaluated according to the following criteria: A: The surface of the paper does not get wet, and the water droplet maintains a high contact angle. B ＋ A: The surface of the paper is slightly wet, but the water droplet maintains a high contact angle. B: The surface of the paper is slightly wet, but the water droplet maintains a high contact angle. C: The surface of the paper is wet, but some of the water droplet remains on the surface without being absorbed. D: The surface of the paper is wet, and the entire water droplet is absorbed by the paper.

[0271] (Oil repellency: TAPPI KIT) For the test paper, the oil resistance (kit method) was evaluated using the following method in accordance with TAPPI KIT-559cm-02, using a test solution (kit test solution) prepared by mixing castor oil, toluene, and heptane in the ratios (volume %) shown in Table 1. Under room temperature conditions, the test paper was placed on a clean, flat, black surface, and one drop of the test solution with the highest kit number was dropped onto the test paper from a height of 13 mm. After 15 seconds, the dropped test solution was removed with clean blotting paper, and the condition of the surface of the test paper that had come into contact with the test solution was visually observed. The first (highest) kit number at which the trace of the dropped liquid disappeared from the surface of the test paper was used as an indicator of oil resistance. A higher number indicates better oil repellency (oil resistance).

[0272]

[0273] (Oil repellency: 60°C soybean oil) A test paper was cut to 5 cm x 5 cm, approximately 0.5 mL of soybean oil was dropped near the center of the test paper, and the paper was placed in an oven and kept at 60°C for 1 hour. After removal, the soybean oil on the test paper was removed. The degree to which the soybean oil soaked into the test paper was then observed visually and evaluated according to the following criteria. In this test, a common vegetable edible oil was used, so oil repellency (oil resistance) under practical usage conditions can be evaluated. A rating of C or higher was considered a pass. A: No trace of oil penetration. B: Trace of oil penetration is only on a part of the surface where the oil was dropped. C: Trace of oil penetration is in multiple places on the surface where the oil was dropped. D: The oil has penetrated and spread throughout the entire test paper.

[0274] (Oil repellency: 80°C soybean oil) The oil repellency test for 60°C soybean oil was carried out in the same manner as before, except that the oven holding time was changed to 80°C, and evaluated according to the following criteria. Note that in cases where the evaluation in the 60°C soybean oil oil oil repellency test was anything other than A, this evaluation may not have been performed. A: No trace of oil penetration. A-: Only one trace of oil penetration with a diameter of 1 mm or less is present on the surface where the oil was dropped. B+: Multiple traces of oil penetration with a diameter of 1 mm or less are present on the surface where the oil was dropped. B: Only one trace of oil penetration with a diameter of more than 1 mm is present on the surface where the oil was dropped. C: Multiple traces of oil penetration with a diameter of more than 1 mm are present on the surface where the oil was dropped. D: Oil has penetrated and spread throughout the entire test paper.

[0275] (Oil repellency: 100°C soybean oil) The oil repellency test for 60°C soybean oil was conducted in the same manner as before, except that the oven holding time was changed to 100°C, and evaluated according to the following criteria. Note that in cases where the evaluation in the 60°C soybean oil oil oil oil repellency test was anything other than A, this evaluation may not have been performed. A: No trace of oil penetration. B ＋ A: Only oil penetration marks less than 1 mm in diameter are present on the surface where the oil was dropped. B: Only one oil penetration mark greater than 1 mm in diameter is present on the surface where the oil was dropped. C: Multiple oil penetration marks greater than 1 mm in diameter are present on the surface where the oil was dropped. D: The oil has penetrated and spread throughout the entire test paper.

[0276] (Oil-repellent stability) The compositions obtained in each example were left to stand in an oven maintained at 45°C for two weeks, and then test papers were obtained using the method described below. The oil-repellent properties (80°C soybean oil) of the obtained test papers were evaluated.

[0277] (Air permeability) Using test paper as a sample, an air permeability evaluation device (Garley Hill S.P.S. Tester, manufactured by Kumagai Riki Kogyo Co., Ltd.) was used to measure the sample surface at 645.16 mm / m². ２ The air permeability was defined as the time (in seconds) required for 100 cc of air to leak through the sample when compressed air was applied vertically to the sample. A lower air permeability indicates better air permeability.

[0278] (Steckihit Size) The size degree (seconds) of the test strip was measured using the Steeckihit method in accordance with JIS P 8122:2004. A longer size degree indicates better water resistance. A value of 5 seconds or more was considered acceptable.

[0279] (Weight-based oil resistance of PTFE filter media) A test specimen was placed on a frosted glass slab. Two 0.75-inch diameter cotton flannel discs were placed in the center of the test specimen, and a 50g weight was placed on the flannel discs. Next, the weight was removed, six drops of castor oil were dropped onto the flannel discs, and the weight was returned to the oil drop site. This state was then maintained at 60°C for one hour. After that, the test specimen was removed from the oven, and the weight, flannel discs, and test specimen were lifted from the frosted glass slab. The condition of the frosted glass slab was visually observed and evaluated according to the following criteria: A: The frosted glass slab is not wet at the oil drop site. B: A portion of the frosted glass slab (less than 40% of the drop site area) is wet at the oil drop site. C: Most of the frosted glass slab (more than 40% of the drop site area) is wet at the oil drop site. D: The frosted glass fragment is wetter than the area where the oil dripped.

[0280] (Antistatic properties of PTFE filter media: Measurement of surface electrical resistivity) To evaluate the surface electrical resistivity of the test specimen (substrate: porous PTFE filter media), measurements were performed in reference to the WSP40.1 standard. The substrate had a particle size of 2 μm and a basis weight of 500 g / m². ２The PTFE filter material was 0.54 mm thick and punched into rectangular pieces with a margin of at least three times the outer diameter of the electrode. The substrate was treated with the oil-repellent composition obtained in each example to obtain test specimens, which were conditioned for more than 24 hours in a constant temperature and humidity chamber at 23 ± 2°C and 50 ± 5% RH. The measuring devices used were the SM-8220 and SME8311 manufactured by HIOKI Corporation. Before measurement, the charge on the sample surface was neutralized with an ionizer and left to stand for 60 seconds. The test specimen was placed on a support stand, the electrodes were brought into contact with a predetermined surface pressure, the external reference electrode was grounded, and the guard electrode was made to follow the potential of the internal measurement electrode. The applied voltage was 100 V under standard conditions, and the surface electrical resistivity was read after 1 minute. The surface electrical resistivity (Ω / sq) at each point was calculated from the measured voltage V and current I at each point using the following formula. ρ_s [Ω / sq] = (2π / ln(r2 / r1)) × (V / I) r1: radius of the inner measuring electrode (center electrode) [cm] r2: inner radius of the outer measuring electrode (ring electrode) (guard electrode follows the potential of the inner measuring electrode) [cm] V: applied voltage (V) I: measured current (A) Measurements were taken at five points on the same sample (center and four points on the periphery), and the average value was used as the measurement result. The measurement results were evaluated according to the following criteria. A: Less than 1.0e10 Ω / sq A-: More than 1.0e10 Ω / sq and less than 5.0e11 Ω / sq B: More than 5.0e11 Ω / sq and less than 1.0e13 Ω / sq C: More than 1.0e13 Ω / sq 1.0e15 Less than Ω / sq D: 1.0e15 Ω / sq or more

[0281] (Oil repellency of PTFE filter material: n-HD) A test specimen was cut into 5 cm x 5 cm pieces, and approximately 0.5 mL of n-HD (n-hexadecane) was dropped near the center of the specimen. After 30 seconds, the n-HD on the test paper was removed. The degree of penetration of n-HD into the test paper was then observed visually and evaluated according to the following criteria: A: No trace of oil penetration. B: Trace of oil penetration is only on a part of the surface where the oil was dropped. C: Trace of oil penetration is in multiple places on the surface where the oil was dropped. D: Oil has penetrated and spread throughout the entire test paper.

[0282] <Raw materials, etc.> (Monomer 1) SIM-500:CH ２ = C(CH ３ )C(O)-O-(CH２ ) ３ [Si(CH ３ ) ２ O] ｎ -Si(CH ３ ) ２ C ４ H ９ (Average molecular weight 500)

[0283] [Synthesis of SIM-500] Prepare a dry three-necked flask (with stirring, thermometer, and dropping funnel) under a nitrogen atmosphere, and prepare hexamethylcyclotrisiloxane ([(CH ３ ) ２ SiO] ３ Dissolve 30.0 g (0.135 mol) of D3 (222.5 g / mol) in 300 mL of anhydrous THF and stir. Slowly add 46.8 mL (0.075 mol) of n-butyllithium (1.6 M hexane solution) dropwise at 0-5°C to suppress exothermic reaction. Then, return the reaction mixture to 25°C and stir under a nitrogen atmosphere for 25 hours to allow ring-opening anionic polymerization to proceed, and the reaction end is converted into living silanolate (-OSi(CH)). ３ ) ２ The reaction was then performed using -Li). Subsequently, at the same temperature (25°C), 36.3 g (approximately 0.165 mol, approximately 2.2 equivalents relative to the BuLi equivalent) of 3-methacryloxypropyldimethylchlorosilane (estimated molecular weight approximately 220 g / mol) and 16.8 g (approximately 0.165 mol, for hydrogen chloride scavenging) were dissolved in a small amount of THF and added dropwise. The mixture was stirred for 1 hour to seal the ends with methacryloxypropyl groups (by-product LiCl was suspended). Then, 5-10 mL of methanol was added to quench the remaining active ends. After diluting the reaction mixture with hexane, LiCl was filtered off, and the filtrate was gradually injected into methanol to precipitate polydimethylsiloxane. The precipitate was collected, washed again with methanol, and dried under reduced pressure at 40°C (overnight). After that, desiccant treatment and solvent removal were performed as necessary. Methacryloxypropyl-terminated polydimethylsiloxane (SIM-500) was obtained by flash column chromatography using silica gel (eluent: hexane / dichloromethane). (Yield: 35 g, yield: 72%)

[0284] TTMSPMA: A compound represented by the following formula (manufactured by Tokyo Chemical Industry Co., Ltd., where X is in formula 1 above)１ is a methacryloyloxy group, A １ is a trimethylene group, B １ (A compound in which the group is represented by the above formula 3)

[0285]

[0286] (Monomer 31) MAA: Methacrylic acid. The solubility of methacrylic acid in water is 10 g / 100 mL. AA: Acrylic acid (miscible in water).

[0287] (Monomer 32) DEAEMA: Diethylaminoethyl methacrylate. The solubility of diethylaminoethyl methacrylate in water is 10 g / 100 mL. DMAEMA: Dimethylaminoethyl methacrylate. The solubility of dimethylaminoethyl methacrylate in water is 11 g / 100 mL. DMAPAA: Dimethylaminopropyl acrylamide (miscible in water). 2-VPy: 2-vinylpyridine. The solubility of 2-vinylpyridine in water is 2.5 g / 100 mL.

[0288] (Monomer 2) PEG-MA23: Polyethylene Glycol Monomethyl Ethyl Methacrylate (n=23), manufactured by TCI (miscible in water). PEG-MA9: Polyethylene Glycol Monomethyl Ethyl Methacrylate (n=9), manufactured by TCI (miscible in water). HEMA: 2-Hydroxyethyl methacrylate (miscible in water). NVF: N-Vinylformamide (miscible in water). NVA: N-Vinylacetamide (miscible in water). AcNHETO-MOI: Compound represented by the following formula (solubility in water of 40 g / 100 mL or more).

[0289]

[0290] [Synthesis of AcNHETO-MOI] 2-Isocyanatoethyl methacrylate (Resonac Co., Ltd. product name "Karens MOI") (16.57 g, 106.8 mmol), tetrahydrofuran (THF) (17.77 g, 246.4 mmol), and dibutyltin dilaurate (DBTDL) (0.061 g, 0.097 mmol) were added to a 100 mL round-bottom flask and stirred in a water bath. 2-Acetamidoethanol (9.30 g, 90.2 mmol) was added dropwise over 20 minutes. After the addition was complete, the mixture was raised to room temperature and stirred for 24 hours. After the reaction was complete, the reaction solution was concentrated, and the resulting mixture was purified by silica gel chromatography (hexane:ethyl acetate = 1:3 followed by 100% ethyl acetate) to obtain AcNHETO-MOI (17.15 g, yield 73.60%). １ H-NMR (400MHz, CDCl ３ ) δ6.48 (m, 1H), 6.12 (t, J = 1.2Hz, 1H), 5.59 (t, J = 1.5Hz, 1H), 5.30 (m, 1H), 4.24 (t, J = 5.5 Hz, 2H), 4.15 (t, J = 5.2Hz, 2H), 3.48 (q, J = 2.5Hz, 4H), 1.97 (s, 3H), 1.93 (q, J = 0.8Hz, 3H)

[0291] (Polymerization solvent) IPA: Isopropyl alcohol acetone

[0292] (Initiators) V-59: Oil-soluble azo polymerization initiator manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. V-601: Oil-soluble azo polymerization initiator manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0293] <(Co)polymer Production> (P1-P53) The monomers, polymerization solvent, and initiator of the type and amount listed in the table were charged into a 1 L or 3 L glass reaction vessel, and the polymerization reaction was carried out at 70°C for 10 hours with stirring under a nitrogen atmosphere to obtain a solution with a solid content of approximately 20% by mass. However, polymer P50 showed gelation of the reaction solution after polymerization.

[0294] <Preparation of test paper or test specimen> (Examples 1-6, 16-17) 150 g of a solution containing the (co)polymer, obtained in the above-described preparation of the (co)polymer, with a solid content of approximately 20%, was taken and diluted with 850 g of isopropanol to prepare a treatment solution (oil-repellent composition) with a copolymer concentration of 3% by mass. The obtained treatment solution was weighed using a bar coat, weighing 40 g / m². ２ After coating bleached non-sized paper, the material was left to stand at room temperature for about 30 minutes, and then dried at 85°C for 10 minutes to obtain test paper (oil-resistant paper). However, in Example 16, test paper could not be produced because copolymer P50 had gelled. The obtained test paper was evaluated according to the evaluations described in each table.

[0295] (Examples 7-13) 150 g of a 20% solids solution containing the copolymer obtained in the above-described production of the (co)polymer was taken and mixed with 20 g of acetic acid to ionize the unit 32 cation donor group in the copolymer to obtain an acetate. This was diluted with 830 g of isopropanol to prepare a treatment solution (oil-repellent composition) with a copolymer concentration of 3% by mass. Test papers were obtained using the obtained treatment solution in the same manner as in Example 1. The obtained test papers were evaluated according to the evaluations described in each table.

[0296] (Examples 14-15) 150 g of a 20% solids solution containing the copolymer obtained in the above-described production of the (co)polymer was taken and mixed with 200 g of a 10% sodium hydroxide aqueous solution to ionize the unit 3 anion donor group in the copolymer to obtain a sodium salt. This was diluted with 650 g of isopropanol to prepare a treatment solution with a copolymer concentration of 3% by mass. Test papers were obtained using the obtained treatment solution in the same manner as in Example 1. The obtained test papers were evaluated according to the table.

[0297] (Examples 18-58) [Ionization and Solvent Removal] The entire volume of the 20% solids solution containing the copolymer obtained in the above-described copolymer production was mixed with an aqueous solution prepared by mixing the acid or base listed in each table with ion-exchanged water to ionize the cation donor group of unit 32 or the anion donor group of unit 31 in the copolymer to form a salt. The polymerization solvent was then removed by vacuum distillation while stirring at 50°C to obtain an aqueous dispersion of the copolymer salt with a solids concentration of approximately 15%.

[0298] [Composition: Copolymer concentration approximately 1.1% by mass, aqueous dispersion with added starch] Hydroxyethylated starch (manufactured by Ingredion, product name "Penford Gum 270") and deionized water were mixed and stirred at 90°C for 30 minutes to obtain an aqueous starch solution with a hydroxyethylated starch concentration of 6% by mass. The obtained aqueous starch solution and an aqueous dispersion containing the copolymer salt obtained by the ionization and desolvation process described above were mixed to a copolymer concentration of approximately 1.1%, and then stirred at 60°C for 10 minutes to obtain a composition (oil-repellent composition). The obtained composition was weighed at a mangle speed of 2.0 m / min and a pressure of 2.0 Bar using a size press, weighing 40 g / m². ２ After treating bleached non-sized paper, test paper (greaseproof paper) was obtained by drying it in a drum dryer at 110°C for 1 minute. The obtained test paper was evaluated according to the criteria described in each table.

[0299] [Composition: Copolymer concentration approximately 0.5% by mass, aqueous dispersion with added starch] A composition was obtained in the same manner as described above for the production of an aqueous dispersion with a copolymer concentration of approximately 1.1% by mass and added starch, except that the copolymer concentration was mixed to 0.5% by mass. The obtained composition was weighed at 40 g / m² using a size press at a mangle speed of 2.0 m / min and a pressure of 2.0 Bar. ２ After treating bleached non-sized paper, test paper (greaseproof paper) was obtained by drying it in a drum dryer at 110°C for 1 minute. The obtained test paper was evaluated according to the criteria described in each table.

[0300] [Composition: Copolymer concentration approximately 0.5% by mass, aqueous dispersion with added PVA] Polyvinyl alcohol (PVA) (Kuraray Co., Ltd., POVA PVA 117) was mixed with ion-exchanged water and stirred at 90°C for 30 minutes to obtain a 1.5% by mass aqueous PVA solution. The obtained aqueous PVA solution and the aqueous dispersion containing the copolymer salt obtained by the above-mentioned ionization and desolvation were mixed so that the copolymer concentration was approximately 0.5% by mass, and then stirred at 60°C for 10 minutes to obtain a composition (oil-repellent composition). The obtained composition was weighed at a mangle speed of 2.0 m / min and a pressure of 2.0 Bar using a size press, weighing 40 g / m². ２ After treating bleached non-sized paper, test paper (greaseproof paper) was obtained by drying it in a drum dryer at 110°C for 1 minute. The obtained test paper was evaluated according to the criteria described in each table.

[0301] [Composition: Aqueous dispersion prepared with water containing approximately 3% by mass of copolymer and pH = 3.58] 1 L of deionized water was maintained at 25°C. A 1.0% (w / v) mother liquor was prepared using food additive grade citric acid (anhydrous equivalent). 8.0 mL of the mother liquor was added under stirring, and after stirring for 3 minutes, pH = 3.58 was confirmed. The aqueous dispersion containing the copolymer salt obtained by ionization and desolvation was mixed with the above-mentioned pH = 3.58 water to a copolymer concentration of approximately 3.0%, and then stirred at 30°C for 10 minutes to obtain the composition (oil-repellent composition). The obtained composition was weighed at 40 g / m² using a size press at a mangle speed of 2.0 m / min and a pressure of 2.0 Bar. ２ After treating bleached non-sized paper, test paper (greaseproof paper) was obtained by drying it in a drum dryer at 110°C for 1 minute. The obtained test paper was evaluated according to the criteria described in each table.

[0302] [Composition: Aqueous dispersion prepared with water containing approximately 3% by mass of copolymer and pH = 7.96] 1 L of deionized water was maintained at 25°C. 5.0 mL of NaHCO3 mother liquor (1% w / v) was added, and after stirring for 3 minutes, pH = 7.96 was confirmed. The aqueous dispersion containing the copolymer salt obtained by ionization and desolvation was mixed with the above-mentioned pH = 7.96 water to a copolymer concentration of approximately 3.0%, and then stirred at 30°C for 10 minutes to obtain the composition (oil-repellent composition). The obtained composition was weighed at 40 g / m² using a size press at a mangle speed of 2.0 m / min and a pressure of 2.0 Bar. ２ After treating bleached non-sized paper, test paper (greaseproof paper) was obtained by drying it in a drum dryer at 110°C for 1 minute. The obtained test paper was evaluated according to the criteria described in each table.

[0303] (Examples 59-60, 76-84) 150 g of a 20% solids solution containing the copolymer obtained in the above-described production of the (co)polymer was taken and mixed with 200 g of a 10% sodium hydroxide aqueous solution to ionize the unit 3 anion donor group in the copolymer to obtain a sodium salt. This was diluted with 650 g of isopropanol to prepare a treatment solution with a copolymer concentration of 3% by mass. The obtained treatment solution was used to evaluate the antistatic properties described above. The obtained treatment solution was also measured by bar coating at a weighing of 300 g / m². ２ After coating a porous material (PTFE filter media), the material was left to stand at room temperature for about 30 minutes, and then dried at 85°C for 10 minutes to obtain test specimens. The weight-based oil resistance (60°C corn oil) and oil repellency (n-HD) of the PTFE filter media were evaluated for the obtained test specimens.

[0304] (Examples 61-75) 150 g of a 20% solids solution containing the copolymer obtained in the above-described production of the (co)polymer was taken and mixed with 20 g of acetic acid to ionize the unit 32 cation donor group in the copolymer to obtain an acetate. This was diluted with 830 g of isopropanol to prepare a treatment solution (oil-repellent composition) with a copolymer concentration of 3% by mass. The obtained treatment solution was used to evaluate the antistatic properties described above. The obtained treatment solution was also measured by bar coating at a weighing of 300 g / m².２ After coating a porous material (PTFE filter media), the material was left to stand at room temperature for about 30 minutes, and then dried at 85°C for 10 minutes to obtain test specimens. The weight-based oil resistance (60°C corn oil) and oil repellency (n-HD) of the PTFE filter media were evaluated for the obtained test specimens.

[0305] (Examples 85-86) 150 g of a solution containing the (co)polymer with a solid content of approximately 20%, obtained in the production of the (co)polymer described above, was taken and diluted with 850 g of isopropanol to prepare a treatment solution (oil-repellent composition) with a copolymer concentration of 3% by mass. The obtained treatment solution was used to evaluate the antistatic properties described above. The obtained treatment solution was also measured by bar coating at a weighing of 300 g / m². ２ After coating the porous material (PTFE filter material), it was left to stand at room temperature for about 30 minutes, and then dried at 85°C for 10 minutes to obtain a test specimen. However, in Example 85, the copolymer P50 had gelled, so a test specimen could not be produced. The weight-based oil resistance (60°C corn oil) and oil repellency (n-HD) of the PTFE filter material were evaluated for the obtained test specimens.

[0306] The table shows the evaluation results for the obtained test strips and test specimens. N.D. indicates that the viscosity was too high to measure.

[0307]

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[0312]

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