Liquid-repellent composition and article

Abstract

Provided is a liquid-repellent composition that exhibits excellent effects in imparting alcohol-repellent properties to a substrate and reducing surface electrical resistance. The liquid-repellent composition contains a non-fluorine copolymer having a unit based on monomer 1 represented by formula 1 and a unit based on monomer 2 having a polymerizable reactive group and a phosphate group. In formula 1, X1 is a monovalent polymerizable reactive group, A1 is a divalent organic group, and B1 is a monovalent organic group having at least one trialkylsilyl group.　(Formula 1) X1-A1-B1

Description

Liquid-repellent compositions and articles

[0001] This disclosure relates to liquid-repellent compositions and articles.

[0002] Medical textile products sometimes require water repellency. In such cases, hydrophobic substrates such as polypropylene nonwoven fabrics are often used. Medical textile products may also require alcohol repellency and antistatic properties. A known method for imparting alcohol repellency is to treat the hydrophobic substrate with a fluorine-based liquid repellent containing a fluorine polymer (Patent Documents 1-2). A known method for imparting antistatic properties is to treat the hydrophobic substrate with an antistatic agent to lower the surface electrical resistance.

[0003] Japanese Patent Publication No. 2018-519430, Japanese Patent Publication No. 2019-196463

[0004] Since antistatic agents are generally hydrophilic, treating a substrate with an antistatic agent tends to reduce its water repellency. Fluorine-based liquid repellents are sometimes used in combination as a means to suppress the reduction in water repellency. However, the fluoropolymers used in fluorine-based liquid repellents raise concerns about their environmental impact. Therefore, there is a need for a liquid repellent composition that contains a non-fluorine polymer with a low environmental impact and can impart alcohol repellency to the substrate and reduce surface resistance. This disclosure provides a liquid repellent composition and articles using the same that are excellent in imparting alcohol repellency to a substrate and reducing surface electrical resistance.

[0005] This disclosure has the following aspects: [1] A liquid repellent composition comprising a non-fluorine copolymer having a unit based on monomer 1 represented by the following formula 1 and a unit based on monomer 2 having a polymerizable reactive group and a phosphate 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. [2] The liquid-repellent composition of [1], wherein monomer 2 is a monomer represented by the following formula 2. ２-A ２ -B ２ ・・・ (Formula 2) In the above Formula 2, X ２ is a monovalent polymerizable reactive group, A ２ is a divalent organic group, B ２ is a phosphate group. [3] The above X １The liquid repellent composition of [1] or [2], wherein the polymerizable reactive group of monomer 2 is independently a polymerizable carbon-carbon double bond group or a hydrolyzable silyl group. [4] The liquid repellent composition of any of [1] to [3], wherein the content of units based on monomer 1 is 50% by mass or more and 99% by mass or less with respect to the total units constituting the nonfluorine copolymer. [5] The liquid repellent composition of any of [1] to [4], wherein the content of units based on monomer 2 is 1% by mass or more and 50% by mass or less with respect to the total units constituting the nonfluorine copolymer. [6] The liquid repellent composition of any of [1] to [5], wherein the total content of units based on monomer 1 and units based on monomer 2 is 51% by mass or more and 100% by mass or less with respect to the total units constituting the nonfluorine copolymer. [7] Any of the liquid-repellent compositions from [1] to [6], wherein the mass ratio of the content of units based on monomer 2 to the content of units based on monomer 1 in the non-fluorine copolymer is 0.01 to 0.50. [8] Any of the liquid-repellent compositions from [1] to [7], wherein monomer 2 is at least one selected from the group consisting of (meth)acryloyloxyalkyl phosphate, (meth)acryloyloxypolyalkylene glycol phosphate, and salts thereof. [9] Any of the liquid-repellent compositions from [1] to [8], wherein the non-fluorine copolymer further comprises units based on halogenated olefins having halogen atoms other than fluorine atoms.

[10] Any of the liquid-repellent compositions from [1] to [9], further comprising an antistatic agent.

[11] Any of the liquid-repellent compositions from [1] to

[10] , further comprising a penetrating agent.

[12] An article obtained by treating a substrate with any of the liquid-repellent compositions from [1] to

[11] .

[13] The article according to

[12] , wherein the base material is a nonwoven fabric.

[14] The article according to

[12] or

[13] , wherein it is for medical use.

[15] Any of the articles according to

[12] to

[14] , having a treated surface having an alcohol repellency of grade 3 or higher as measured by the AATCC test method TM193 Aqueous Liquid Repellency:Water / Alcohol Solution Resistance Test and a surface electrical resistance of 100 GΩ or less.

[0006] According to this disclosure, it is possible to provide a liquid-repellent composition and an article using the same that have excellent effects in imparting alcohol repellency to a substrate and reducing surface electrical resistance.

[0007] The meanings and definitions of terms used in this disclosure are as follows: "Non-fluorinated copolymer" is a copolymer that does not contain fluorine atoms. "Fluorine atom-free" means that the fluorine atom content relative to the total mass of the copolymer is 0.1% by mass or less, preferably 0% by mass. The fluorine atom content relative to the total mass of the copolymer can be measured by combustion ion chromatography or the like. "Monomer-based unit" is an atomic group of a structure formed by the polymerization of one monomer molecule. The unit may be an atomic group directly formed by the polymerization of monomers, or it may be an atomic group obtained by chemically transforming a part of an atomic group formed by the polymerization of another monomer with a partially different structure. "(meth)acrylate" is a general term for acrylate and methacrylate. Similarly, "(meth)acryloyl(oxy) group" is a general term for acryloyl(oxy) group and methacryloyl(oxy) 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. 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.

[0008] <<Liquid-Repellent Composition>> A liquid-repellent composition according to one embodiment of the present disclosure comprises a non-fluorine copolymer (hereinafter also referred to as "Copolymer A"). The liquid-repellent composition may contain a liquid medium. The liquid-repellent composition may contain other components as needed. The liquid-repellent composition may be the solution or dispersion obtained by the method for producing copolymer A described later, or it may be a liquid obtained by further diluting the above solution or dispersion, or it may be a liquid obtained by adding other components to the above solution, dispersion, or diluted liquid therefor.

[0009] <Copolymer A> Copolymer A has units based on monomer 1 (hereinafter also referred to as "unit 1") and units based on monomer 2 (hereinafter also referred to as "unit 2"). Copolymer A may also have units based on halogenated olefins having halogen atoms other than fluorine atoms (hereinafter also referred to as "monomer 3") (hereinafter also referred to as "unit 3"). Copolymer A may also have units based on reactive monomers (hereinafter also referred to as "monomer 4") (hereinafter also referred to as "unit 4"). Copolymer A may also have units based on monomers other than monomers 1 to 4 (hereinafter also referred to as "monomer 5") (hereinafter also referred to as "unit 5").

[0010] (Unit 1) Monomer 1 is a monomer represented by the following equation 1. １ -A １ -B １ ...(Formula 1) In Formula 1, X １ A is a monovalent polymerizable reactive group, １ is a divalent organic group, B １ This is a monovalent organic group having at least one trialkylsilyl group.

[0011] [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.

[0012] In 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 other than a fluorine atom, or a monovalent hydrocarbon group which may be halogenated with a halogen other than fluorine.

[0013] R １０１ ~R １０５ In this, a monovalent hydrocarbon group is preferably an alkyl group having 1 to 4 carbon atoms. １０１ ~R １０５ Of these, R １ Those that are not bonded to the other are preferably monovalent hydrocarbon groups that may be halogenated with a hydrogen atom or a halogen other than fluorine, and more preferably hydrogen atoms.

[0014] * Ａ１ -R １１ C(=O)CR １３ =CH ２ ...(Formula 6) In Formula 6, R １１ is a single bond, oxygen atom, or NR １２ It is a divalent group represented by R １３ * is a hydrogen atom, a halogen atom other than a fluorine atom, or a linear or branched alkyl group having 1 to 12 carbon atoms. Ａ１ - is A １ This is a combination of R. １２ This is a hydrogen atom or a monovalent organic group.

[0015] R １１ is an oxygen atom, or NR １２ A divalent group represented by R is preferred. １２The monovalent organic groups in this include linear or branched alkyl groups having 1 to 12 carbon atoms, and -A １ -B １ Examples include: A １ and B １ These are A in Equation 1, respectively. １ and B １ It is similar to 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 The 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, R １３ When is a hydrogen atom or a methyl group, formula 6 represents a (meth)acryloyloxy group. １１ NR １２ A divalent group represented by R １３ When is a hydrogen atom or a methyl group, formula 6 represents a (meth)acrylamide group. The monovalent group represented by formula 6 is preferably a (meth)acryloyloxy group or a (meth)acrylamide group.

[0016] Examples of hydrolyzable silyl groups include the monovalent group represented by formula 7 below.

[0017] * Ａ１ -SiR １４ ３－ａ X ａ ... (Equation 7) In Equation 7, a is an integer of 2 or 3. X represents a hydroxyl group, a halogen atom other than a fluorine atom, or a hydrolyzable group. Multiple Xs may be the same or different. R １４ This refers to a monovalent organic group having 1 to 20 carbon atoms, and represents an organic group other than the hydrolyzable group in X. * Ａ１ - is A １ This is a combination of the two.

[0018] 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 due to their mild hydrolysis and ease of handling. Methoxy groups, ethoxy groups, and isopropoxy groups are preferred as alkoxy groups, with methoxy groups and ethoxy groups being more preferred. When the alkoxy group is a methoxy group or an ethoxy group, siloxane bonds are readily formed.

[0019] R １４ Examples of hydrolyzable groups in "organic groups other than hydrolyzable groups" are those similar to the hydrolyzable groups in X. １４ Preferably, alkyl groups, cycloalkyl groups, aryl groups, α-chloroalkyl groups, and triorganosiloxy groups are used, and more preferably 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 are used.

[0020] Examples of hydrolyzable silyl groups represented by formula 7 include trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, tris(2-propenyloxy)silyl, triacetoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethylsilyl, methyldiisopropoxysilyl, (α-chloromethyl)dimethoxysilyl, and (α-chloromethyl)diethoxysilyl. Among these, trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, and diethoxymethylsilyl are preferred, with dimethoxymethylsilyl being more preferred.

[0021] [Divalent organic group: A] １ ] A １As the divalent organic group, a divalent hydrocarbon group is preferred. Examples of divalent hydrocarbon groups include linear or branched alkylene groups, cycloalkylene groups, groups in which at least one of the carbon-carbon single bonds of the alkylene group is replaced with a carbon-carbon double bond or a carbon-carbon triple bond (e.g., alkenylene group, alkylylene group), groups in which at least one of the carbon-carbon single bonds of the cycloalkylene group is replaced with a carbon-carbon double bond, and arylene groups. Among these, linear or branched alkylene groups and cycloalkylene groups are preferred, linear or branched alkylene groups are more preferred, and linear alkylene groups are even more preferred. The carbon in the divalent hydrocarbon group may be replaced with a heteroatom or a divalent group having a heteroatom. The hydrogen in the hydrocarbon group may be replaced with a halogen atom or a monovalent group having a heteroatom. Examples of heteroatoms include nitrogen, oxygen, sulfur, boron, and phosphorus atoms, with nitrogen and oxygen atoms being preferred. Examples of divalent groups having heteroatoms include amide groups, urethane groups, urea groups, carbonyl groups, and ester groups. Examples of monovalent groups having heteroatoms include hydroxyl groups, mercapto groups, amino groups, and monovalent groups including the divalent groups having heteroatoms mentioned above. A １ It does not contain silicon atoms.

[0022] A １ The number of carbon atoms is preferably 2 to 20, more preferably 2 to 16, even more preferably 2 to 10, and particularly preferably 2 to 6.

[0023] A １ Preferably, the alkylene group is a linear alkylene group having 1 to 8 carbon atoms, such as a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, and octylene group; more preferably, a branched alkylene group in which at least one hydrogen atom of the linear alkylene group is substituted with an alkyl group having 1 to 3 carbon atoms, such as a methyl group, ethyl group, and propyl group; and more preferably, the linear alkylene group. １ Specific examples include: Ｘ１＊ - [CH ２ C(O)NH] ｎ１ (CH ２ ) ３- ＊Ｂ１ and Ｘ１＊ -[CH ２ C(O)NH] ｎ１ CH ２ CH(CH ３ )- ＊Ｂ１ are exemplified, Ｘ１＊ -(CH ２ ) ３ - ＊Ｂ１ is preferred. n1 in the specific examples of A １ is an integer of 0 to 3, and an integer of 0 to 2 is preferred. Ｘ１＊ - is a bond with X １ , and - ＊Ｂ１ is a bond with B １ .

[0024] [Monovalent organic group having at least one trialkylsilyl group: B １ The number of trialkylsilyl groups in B １ is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 3. Further, as one embodiment of the present disclosure, the number of trialkylsilyl groups in B １ is also preferably 2 to 9, more preferably 2 to 6, and even more preferably 2 to 3. When the number of trialkylsilyl groups is within the above range, the oil repellency of the article treated with the copolymer A is more excellent. When B １ has two or more trialkylsilyl groups, the plurality of trialkylsilyl groups may be the same or different from each other.

[0025] As the alkyl group of the trialkylsilyl group, a linear or branched alkyl group having 1 to 6 carbon atoms is preferred, a t-butyl group, an isopropyl group, an ethyl group, and a methyl group are more preferred, an ethyl group and a methyl group are even more preferred, and a methyl group is particularly preferred. The three alkyl groups of the trialkylsilyl group may be the same or different from each other.

[0026] B １ preferably has a siloxane bond. B １The number of Si-O bonds in the copolymer is preferably 1 to 80, more preferably 1 to 20, even more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 2 to 5. When the number of Si-O bonds is within the above range, the oil repellency of the article treated with copolymer A is better. B １ The silicon number is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 8, even more preferably 1 to 6, particularly preferably 2 to 5, and most preferably 3 to 4.

[0027] A １ B combines with １ The atom inside is preferably a silicon atom. B １ Preferably, the monovalent organic group represented by formula 3 below or the monovalent organic group represented by formula 4 below is preferred, and the monovalent organic group represented by formula 3 below is more preferred. In formulas 3 and 4 below, Ａ１ *- is A １ This is a combination of the two.

[0028] Ａ１ *-Si(OSiR １５ ３ ) ３－ｂ R １６ ｂ ...Equation 3 In Equation 3, b is an integer between 0 and 2. 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. １５１ Each of these is independently a linear or branched alkyl group having 1 to 6 carbon atoms, and R １５２ R is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, １５３ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms, where c is an integer from 0 to 2. １６ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms. Ａ１＊ - is A １ This is a combination of the two.

[0029] ​b is preferably 0 or 1, and particularly preferably 0. １５ , R １５１ , R １５３ and R １６ The linear or branched alkyl group in formula 3 is preferably a t-butyl group, an isopropyl group, an ethyl group, and a methyl group, more preferably an ethyl group and a methyl group, and even more preferably a methyl group. １５ and R １６ If there are multiple, R １５ and R １６ These may be the same or different. １５２ In formula 3, the linear or branched alkylene group is preferably a methylene group or an ethylene group, and more preferably an ethylene group. c is preferably 0. In formula 3, multiple R １５ These may be the same or different. １５ ga-OSiR １５１ ３ If so, multiple R １５１ These may be the same or different. If b is 2, there are multiple R １６ These can be the same or different. If c is 2, there are multiple R １５３ These may be the same or different. In one preferred embodiment, R １５ and R １６ Each of these is an independent linear or branched alkyl group having 1 to 6 carbon atoms.

[0030] Ａ１ *-SiR １７ ２ (OSiR １８ ２ ) ｎ OSiR １９ ３ ...Formula 4 In 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. n is an integer greater than or equal to 0. Ａ１＊ - is A １ This is a combination of the two.

[0031] From the viewpoint of oil repellency, n is preferably an integer between 0 and 10, more preferably an integer between 0 and 6, and even more preferably an integer between 0 and 3.​１７ , R １８ and R １９ The linear or branched alkyl group in is preferably a t-butyl group, isopropyl group, ethyl group, and methyl group, more preferably ethyl group and methyl group, and even more preferably methyl group. １７ , R １８ and R １９ These may be the same or different.

[0032] As the monovalent organic group represented by formula 3 above, the monovalent organic group represented by formula 31 or 32 below is preferred. In formula 31 or 32, Ａ１ *- is A １ This is a combination of the two.

[0033]

[0034] As the monovalent organic group represented by formula 4 above, the monovalent organic group represented by formula 41 below is preferred. In formula 41, Ａ１ *- is A １ This is a combination of the two.

[0035] In equation 41, n is the same as n in equation 4.

[0036] 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 to 450, 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 to 450. 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 1,000.

[0037] 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, and N-(tris(trimethylsiloxy)silylpropyl)(meth)acrylamide, with 3-((meth)acryloyloxy)propyltris(trimethylsiloxy)silane, 3-((meth)acryloyloxy)propylbis(trimethylsiloxy)methylsilane, and N-(tris(trimethylsiloxy)silylpropyl)(meth)acrylamide being more preferred.

[0038] Monomer 1 may be used alone or in combination of two or more types.

[0039] (Unit 2) Monomer 2 is a monomer having polymerizable reactive groups and phosphate groups. Monomer 2 may have multiple polymerizable reactive groups and multiple phosphate groups.

[0040] Examples of polymerizable reactive groups of monomer 2 include groups having polymerizable carbon-carbon double bonds and hydrolyzable silyl groups, with groups having polymerizable carbon-carbon double bonds being preferred. The groups having polymerizable carbon-carbon double bonds and hydrolyzable silyl groups are each represented by 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 X １ If is a group having a polymerizable carbon-carbon double bond, then it is preferable that the polymerizable reactive group of monomer 2 is also a group having a polymerizable carbon-carbon double bond. In this case, X １ The polymerizable carbon-carbon double bond group of monomer 2 may be the same or different, but it is preferable that they be the same. １ If is a hydrolyzable silyl group, then the polymerizable reactive group of monomer 2 is also preferably a hydrolyzable silyl group. In this case, X １ The hydrolyzable silyl groups of monomer 2 may be the same or different, but it is preferable that they be the same.

[0041] The phosphate group is -O-P(=O)(OH) ２It is represented as follows. The phosphate group may react with a base to form a salt. Examples of salts include alkanolamine salts such as monoethanolamine salts and diethanolamine salts, alkali metal salts, and alkaline earth metal salts.

[0042] The monomer 2 is preferably the monomer represented by the following formula 2. ２ -A ２ -B ２ ...(Formula 2) In Formula 2, X ２ A is a monovalent polymerizable reactive group, ２ is a divalent organic group, B ２ It is a phosphate group.

[0043] X ２ Polymerizable reactive group, B ２ The phosphate groups are the same as the polymerizable reactive group and phosphate group of monomer 2 described above. ２ As for the divalent organic group, A １ Examples of groups similar to the divalent organic groups explained above are given. A ２ For example, -R ２４ - or - (R ２５ O) ｐ -R ２４ A group represented by - is preferred. ２４ and R ２５ Each of these is an independent alkylene group, and p is an integer from 1 to 20. When p is 2 or greater, there are p R ２５ These may be the same or different. p is more preferably 1 to 10, even more preferably 1 to 8, and particularly preferably 1 to 5. R ２４ and R ２５ The alkylene group in is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more 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, and more preferably a branched alkylene group in which at least one hydrogen atom of the linear alkylene group is substituted with an alkyl group having 1 to 3 carbon atoms such as a methyl group, ethyl group, or propyl group, and also preferably an ethylene group or a propylene group (-CH ２ CH (CH ３ )-) is particularly preferable. Therefore, R２５ As for O, CH ２ CH ２ O or CH ２ CH (CH ３ )O is particularly preferred.

[0044] Examples of monomer 2 include (meth)acryloyloxyalkyl phosphate, (meth)acryloyloxypolyalkylene glycol phosphate, and salts thereof. (meth)acryloyloxyalkyl phosphate is represented by X in formula 2 above. ２ is a (meth)acryloyloxy group, A １ ga-R ２４ - A compound that is - is an example. (meth)acryloyloxypolyalkylene glycol phosphate is X in formula 2 above. ２ is a (meth)acryloyloxy group, A １ ga- (R ２５ O) ｐ -R ２４ Examples of compounds that fit this description include (meth)acryloyloxyalkyl phosphates, (meth)acryloyloxypolyalkylene glycol phosphates, and their salts. Specific examples include (meth)acryloyloxyethyl phosphate, (meth)acryloyloxypolyethylene glycol phosphate, (meth)acryloyloxyethyl phosphate monoethanolamine half-salt, and (meth)acryloyloxypolypropylene glycol phosphate. Preferred monomers are (meth)acryloyloxyethyl phosphate, (meth)acryloyloxypolyethylene glycol phosphate, and (meth)acryloyloxypolypropylene glycol phosphate, with (meth)acryloyloxyethyl phosphate being more preferred. Monomer 2 may be used alone or in combination of two or more.

[0045] (Unit 3) Monomer 3 is a halogenated olefin having halogen atoms other than fluorine atoms. When copolymer A has unit 3, a dense water-repellent and oil-repellent film is more easily formed on the surface of the article, thus improving the initial water-repellency and oil-repellency. In addition, as a result of improved adhesion to the article being treated, the water-repellency and oil-repellency are less likely to decrease due to abrasion, and the durability against abrasion (hereinafter also referred to as "abrasion durability") is improved.

[0046] The monomer 3 is preferably vinyl halide or vinylidene halide having one or two halogen atoms, and more preferably vinylidene halide having two halogen atoms. The halogen atoms of monomer 3 are preferably chlorine, bromine, and iodine atoms, more preferably chlorine and bromine atoms, and even more preferably chlorine atoms. When monomer 3 has two or more halogen atoms, the multiple halogen atoms may be the same or different. The monomer 3 is preferably vinyl chloride and vinylidene chloride, and more preferably vinylidene chloride. Monomer 3 may be used alone or in combination of two or more types.

[0047] (Unit 4) Monomer 4 is a reactive monomer. A reactive monomer is a monomer other than monomers 1, 2, and 3 that has two or more polymerizable reactive groups, or has a crosslinkable functional group and a polymerizable reactive group. When copolymer A has unit 4, reactions (e.g., crosslinking reactions) occur between the article treated with copolymer A and unit 4, and between copolymer A itself, resulting in improved liquid repellency against prolonged contact with liquids and durability against washing, etc., of the article treated with copolymer A.

[0048] Examples of polymerizable reactive groups include groups having polymerizable carbon-carbon double bonds and hydrolyzable silyl groups, with groups having polymerizable carbon-carbon double bonds being preferred. The groups having polymerizable carbon-carbon double bonds and hydrolyzable silyl groups are each represented by 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.

[0049] Preferred crosslinkable functional groups include functional groups having at least one of the following bonds: covalent bonds, ionic bonds, and hydrogen bonds, and functional groups that can form a crosslinked structure through the interaction of these bonds. For example, isocyanate groups, blocked isocyanate groups, alkoxysilyl groups, primary amino groups, alkoxymethylamide groups, silanol groups, primary amide groups, epoxy groups, hydroxyl groups, oxazoline groups, carboxyl groups, and sulfonic acid groups are preferred, isocyanate groups, blocked isocyanate groups, hydroxyl groups, primary amino groups, and epoxy groups are more preferred, and blocked isocyanate groups are particularly preferred.

[0050] The blocked isocyanate group is represented by formula 9 below: -N(H)-C(=O)-X ４ ...Formula 9

[0051] In formula 9, X ４ X represents a monovalent organic group and is a protecting group. ４ The group can be any group capable of protecting the isocyanate group. ４ The number of carbon atoms is preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 6.

[0052] X ４ It is preferable that it has heteroatoms. Examples of heteroatoms include nitrogen atoms, oxygen atoms, and sulfur atoms, with nitrogen atoms and oxygen atoms being preferred. The number of heteroatoms is preferably 1 to 4, and more preferably 1 to 2. X bonded to the carbon atom in formula 9 ４ The atoms inside are preferably heteroatoms, and more preferably nitrogen atoms.

[0053] X ４Preferred pyrazole compounds include monovalent groups obtained by removing hydrogen from the NOH group of an oxime compound, monovalent groups obtained by removing hydrogen from the NH group of a pyrazole compound, and monovalent groups obtained by removing hydrogen from the NH group of an ε-caprolactam compound. 2-butanone oxime is preferred as the oxime compound. Pyrazole compounds include pyrazole and pyrazole derivatives in which hydrogen atoms bonded to carbon atoms in pyrazole are substituted with alkyl groups. 3-methylpyrazole and 3,5-dimethylpyrazole are preferred as pyrazole derivatives. ε-caprolactam compounds include ε-caprolactam and ε-caprolactam derivatives in which hydrogen atoms bonded to carbon atoms in ε-caprolactam are substituted with alkyl groups.

[0054] X ４ More preferably, the group is selected from a monovalent group obtained by removing hydrogen from the NOH or NH group of any one compound selected from the group consisting of 2-butanone oxime, pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, and ε-caprolactam, and even more preferably, the group is selected from a monovalent group obtained by removing hydrogen from the NH group of any one compound selected from the group consisting of 3-methylpyrazole, 3,5-dimethylpyrazole, and ε-caprolactam.

[0055] Preferred monomers 4 include (meth)acrylates having crosslinkable functional groups, (meth)acrylamides having crosslinkable functional groups, vinyl ethers having crosslinkable functional groups, vinyl esters having crosslinkable functional groups, (meth)acrylates having two or more polymerizable reactive groups, and (meth)acrylamides having two or more polymerizable reactive groups.

[0056] Examples of monomer 4 include, but are not limited to, the following compounds.

[0057] 2-Butanone oxime adduct of 2-isocyanatoethyl (meth)acrylate (2-[0-(1'-methylpropyleneneamino)carboxyamino]ethyl (meth)acrylate), pyrazole adduct of 2-isocyanatoethyl (meth)acrylate, 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate), 3-methylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate, ε-caprolactam adduct of 2-isocyanatoethyl (meth)acrylate, 2-Butanone oxime adduct of 3-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl Pyrazole adducts of pyr (meth)acrylate, 3,5-dimethylpyrazole adduct of 3-isocyanatopropyl (meth)acrylate, 3-methylpyrazole adduct of 3-isocyanatopropyl (meth)acrylate, ε-caprolactam adduct of 3-isocyanatopropyl (meth)acrylate, 2-butanone oxime adduct of 4-isocyanatobutyl (meth)acrylate, pyrazole adduct of 4-isocyanatobutyl (meth)acrylate, 3,5-dimethylpyrazole adduct of 4-isocyanatobutyl (meth)acrylate, 3-methylpyrazole adduct of 4-isocyanatobutyl (meth)acrylate, and ε-caprolactam adduct of 4-isocyanatobutyl (meth)acrylate.

[0058] 2-Isocyanatoethyl (meth)acrylate, 3-Isocyanatopropyl (meth)acrylate, 4-Isocyanatobutyl (meth)acrylate. Methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, butoxymethyl (meth)acrylamide, diacetone acrylamide, γ-methacryloyloxypropyltrimethoxysilane, trimethoxyvinylsilane, vinyltrimethoxysilane.

[0059] t-butyl(meth)acrylamide sulfonic acid, (meth)acrylamide, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, diacetone(meth)acrylamide, glycidyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 3-chloro-2-hydroxypropyl methacrylate, polyoxyalkylene Polycaprolactone esters of glycol mono(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl(meth)acrylate, (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyhexahydrophthalic acid, 2-(meth)acryloyloxyethyl acid phosphate, allyl(meth)acrylate, 2-vinyl-2-oxazoline, and 2-vinyl-4-methyl-(2-vinyloxazoline)hydroxyethyl(meth)acrylate.

[0060] Tri(meth)allyl isocyanurate (Nippon Kasei Co., Ltd. product), triallyl cyanurate (TAC, Nippon Kasei Co., Ltd. product), 3-(methylethyl ketoxime) isocyanatomethyl-3,5,5-trimethylcyclohexyl(2-hydroxyethyl methacrylate) cyanate (Teccoat HE-6P, Kyoken Kasei Co., Ltd. product), polycaprolactone ester of hydroxyethyl (meth)acrylate (Praxel FA, FM series, Daicel Chemical Industries, Ltd. product).

[0061] 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 diglycidyl di(meth)acrylate, 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 Sulfate, 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, 2-(((2-((meth)acryloyloxy)ethyl)carbamoyl)oxy)ethyl methacrylate.

[0062] These are multifunctional urethane acrylates manufactured by Daicel Ornex Co., Ltd.: 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).

[0063] N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, 1,3,5-tri(meth)acryloylhexahydro-1,3,5-triazine.

[0064] Preferred monomers 4 include 2-[0-(1'-methylpropyleneneamino)carboxyamino]ethyl (meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, N-methylol (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, 3-chloro-2-hydroxypropyl methacrylate, and polycaprolactone esters of hydroxyethyl (meth)acrylate (Praxel FA, FM series products of Daicel Chemical Industries, Ltd.). Monomer 4 may be used alone or in combination of two or more.

[0065] (Unit 5) Monomer 5 is a monomer other than monomer 1, monomer 2, monomer 3, and monomer 4. It is preferable that monomer 5 has a polymerizable reactive group. Examples of polymerizable reactive groups include a group having a polymerizable carbon-carbon double bond and a hydrolyzable silyl group, with a group having a polymerizable carbon-carbon double bond being preferred. The group having a polymerizable carbon-carbon double bond and the hydrolyzable silyl group are each represented by 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 above. Monomer 5 may have two or more polymerizable reactive groups, and the two or more polymerizable reactive groups may be the same or different.

[0066] X １ and X ２If the polymerizable group has a polymerizable carbon-carbon double bond, it is preferable that the polymerizable reactive group of monomer 5 also has a polymerizable carbon-carbon double bond. １ , X ２ The polymerizable carbon-carbon double bond groups of monomer 5 may be the same or different, but it is preferable that they be the same.

[0067] X １ and X ２ If the polymerizable reactive group is a hydrolyzable silyl group, then the polymerizable reactive group of monomer 5 is also preferably a hydrolyzable silyl group. １ , X ２ The hydrolyzable silyl groups of monomer 5 may be the same or different, but it is preferable that they be the same.

[0068] Monomer 5 having a polymerizable carbon-carbon double bond as a polymerizable reactive group includes, but is not limited to, monomers 1, 2, 3, and 4, vinyl carboxylates, allyl carboxylates, vinyl ethers, allyl ethers, olefin compounds, styrene compounds, (meth)acrylates, (meth)acrylic acid, (meth)acrylamide compounds, and other vinyl compounds.

[0069] Examples of vinyl carboxylate esters include vinyl acetate, vinyl pivalate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl octoate, vinyl monochloroacetate, vinyl methacrylate, vinyl crotate, and vinyl cinnamate. An example of an allyl carboxylate ester is allyl acetate.

[0070] Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, stearyl vinyl ether, chloromethyl vinyl ether, 2-chloroethyl vinyl ether, chloropropyl vinyl ether, and cyclohexyl vinyl ether.

[0071] An example of an allyl ether is allyl ethyl ether.

[0072] Examples of olefin compounds include ethylene and propylene.

[0073] Examples of styrene-based compounds include styrene, 4-chlorostyrene, 4-methylstyrene, and 4-methoxystyrene.

[0074] Examples of (meth)acrylates 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.), aromatic (meth)acrylates (phenyl (meth)acrylate, benzyl (meth)acrylate, etc.), aliphatic cyclic (meth)acrylates (cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, etc.), N,N-diisopropylaminoethyl (meth)acrylate, stearamide ethyl (meth)acrylate, stearamide propyl (meth)acrylate, behenamide ethyl (meth)acrylate, and behenamide propyl (meth)acrylate.

[0075] Examples of (meth)acrylamide compounds include alkyl (meth)acrylamides (N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N-(n-butyl)(meth)acrylamide, N-(t-butyl)(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, N-lauryl(meth)acrylamide, N-stearyl(meth)acrylamide, 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.), and (meth)acrylamides in which the nitrogen atom forms a heterocyclic structure (N-(meth)acryloylmorpholine, N-(meth)acryloylpiperidine, etc.).

[0076] Other vinyl compounds include, for example, trimethylvinylsilane.

[0077] Examples of monomers 5 having a hydrolyzable silyl group as a polymerizable reactive group include compounds in which the polymerizable reactive group of monomer 5 having a polymerizable carbon-carbon double bond as described above is substituted with a hydrolyzable silyl group.

[0078] (Composition of the copolymer) The content of unit 1 relative to the total units constituting copolymer A is preferably 50 to 99% by mass, more preferably 60 to 98% by mass, even more preferably 70 to 97% by mass, and particularly preferably 80 to 96% by mass. It is considered that when the content of unit 1 is above the lower limit of the above, the alcohol-repellent properties and the effect of reducing surface electrical resistance are better.

[0079] The content of unit 2 relative to the total units constituting copolymer A is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, even more preferably 1 to 10% by mass, and particularly preferably 1 to 5% by mass. It is believed that if the content of unit 2 is above the lower limit, the effect of reducing the surface electrical resistance is better, and if it is below the upper limit, the alcohol repellency is better.

[0080] The total content of unit 1 and unit 2 relative to the total units constituting copolymer A is preferably 51 to 100% by mass, more preferably 61 to 100% by mass, even more preferably 71 to 100% by mass, and particularly preferably 81 to 100% by mass.

[0081] In copolymer A, the mass ratio of the content of unit 2 to the content of unit 1 (unit 2 / unit 1) is preferably 0.01 to 0.50, more preferably 0.02 to 0.20, even more preferably 0.05 to 0.15, particularly preferably 0.05 to 0.10, and most preferably 0.050 to 0.060, from the viewpoint of balancing alcohol repellency, surface electrical resistance reduction effect, and water pressure resistance.

[0082] When copolymer A contains unit 3, the content of unit 3 relative to the total units constituting copolymer A is preferably 1 to 35% by mass, more preferably 5 to 25% by mass, and even more preferably 10 to 20% by mass.

[0083] When copolymer A contains unit 4, the content of unit 4 relative to the total units constituting copolymer A is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 1 to 4% by mass.

[0084] When copolymer A contains unit 5, the content of unit 5 relative to the total units constituting copolymer A is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, even more preferably 1 to 30% by mass, and particularly preferably 1 to 20% by mass.

[0085] The content of each unit is: １ The reaction rates of monomers 1 to 5 can be calculated by H-NMR, gas chromatography, and high-performance liquid chromatography. When copolymer A is produced, if the conversion rate of monomers 1 to 5 to copolymer A is high (for example, 90% or more), the content of each unit may be calculated based on the amount of monomers 1 to 5 charged.

[0086] Units 1 to 5 may form random copolymers or block copolymers. Copolymer A may contain two or more types of unit 1. Copolymer A may contain two or more types of unit 2. If copolymer A contains unit 3, there may be two or more types of unit 3. If copolymer A contains unit 4, there may be two or more types of unit 4. If copolymer A contains unit 5, there may be two or more types of unit 5.

[0087] The manganese (Mn) of copolymer A is preferably 1,000 to 1,000,000, more preferably 10,000 to 1,000,000, and even more preferably 10,000 to 800,000. When the Mn of copolymer A is above the lower limit, the liquid repellency of the article treated with copolymer A is better. When the Mn of copolymer A is below the upper limit, the dispersibility in various solvents is better.

[0088] The Mw of copolymer A is preferably 1,000 to 1,000,000, more preferably 10,000 to 1,000,000, and even more preferably 10,000 to 800,000. When the Mw of copolymer A is above the lower limit, the liquid repellency of the article treated with copolymer A is better. When the Mw of copolymer A is below the upper limit, the dispersibility in various solvents is better.

[0089] <Method for producing copolymer A> Copolymer A can be produced, for example, by polymerizing monomer 1, monomer 2, and, if necessary, at least one selected from the group consisting of monomers 3 to 5. The amounts of monomers 1 to 5 to be charged should be appropriately set to satisfy the composition of copolymer A.

[0090] (Initiators) When polymerizing monomers 1 to 5, it is preferable to use an initiator. There are no particular restrictions on the initiator, and it can be appropriately selected depending on the type of polymerizable reactive group of monomers 1 to 5. 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 that generate these in the polymerization system, etc., used in cationic polymerization; and organometallic compounds and photoanionic polymerization initiators that generate organic bases in the polymerization system, etc., used in anionic polymerization. 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. As azo polymerization initiators, commercially available products such as V-59, V-601, V-65, VA-057, and VA-061 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) can also be used. There are no particular restrictions on organic acids, for example, methanesulfonic acid. There are no particular restrictions on inorganic acids, for example, hydrochloric acid, nitric acid, and sulfuric acid. There are no particular restrictions on Lewis acids, for example, trichloroaluminum, ethylaluminum dichloride, and ethylaluminum sesquichloride.There are no particular restrictions on the thermal cationic polymerization initiator; for example, benzyl(4-hydroxyphenyl)methylsulfonium hexafluoroantimonate. There are no particular restrictions on the photocationic 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 available. There are no particular restrictions on the organometallic compounds; for example, n-butyllithium, sec-butyllithium, t-butyllithium, diethylzinc, and triethylaluminum are available. There are no particular restrictions on the photoanionic polymerization initiator; for example, commercially available products such as WPBG-266, WPBG-300, and WPBG-345 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) are available.

[0091] 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 monomers 1 to 5. 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.

[0092] (Molecular weight modifiers) Molecular weight modifiers may be used when polymerizing monomers 1 to 5. Preferred molecular weight modifiers include aromatic compounds, mercapto alcohols, and mercaptocarboxylic acids and alkyl mercaptans, with mercaptocarboxylic acids and 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 monomers 1 to 5 in total.

[0093] (Chain Transfer Agent) When polymerizing monomers 1 to 5, a chain transfer agent that enables living radical polymerization may be used for further molecular weight control. Reversible addition-cleavage chain transfer agents are preferred as chain transfer agents, and examples include cyanomethyl dodecyltrithiocarbonate, 2-cyano-2-propylbenzodithioate, 2-(dodecylthiocarbonothiothio)-2-methylpropanoic acid, and cyanomethyl methyl(phenyl)carbamodithioate. In particular, when monomers having two or more polymerizable groups in one molecule are used for polymerization, adding such a chain transfer agent is preferable because it can suppress gelation and precipitation of copolymer A. 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 of monomers 1 to 5.

[0094] (Catalyst) A catalyst may be used to obtain copolymer A. 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 of monomers 1 to 5.

[0095] (Polymerization 1) When the polymerizable reactive groups of monomers 1 to 5 are groups having polymerizable carbon-carbon double bonds, copolymer A having units 1 to 5 is obtained by polymerizing monomers 1 to 5 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 more preferably to use an azo compound.

[0096] 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 without the use of emulsifiers, making it easier to control the composition and less likely to introduce impurities.

[0097] Organic solvents are preferred as the medium used in solution polymerization. The organic solvent is not particularly limited as long as the monomer is soluble; 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] There are no particular restrictions on the ether-based organic solvents, and examples include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dibutyl ether, diethylene glycol methyl ethyl ether, and tetrahydrofuran. These may be used individually or in combination of two or more.

[0102] There are no particular restrictions on the ester-based organic solvents, and examples include methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxypropionate, cyclohexanol acetate, γ-butyrolactone, 3-methyl-3-methoxybutyl acetate, and glycerin triacetate. These may be used individually or in combination of two or more.

[0103] In the emulsion polymerization method, for example, monomers 1 to 5 are polymerized in an emulsion containing monomers 1 to 5, 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. Preferably, the water-soluble organic solvent is at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols, and aprotic polar solvents. When the aqueous medium contains a water-soluble organic solvent, the content of the water-soluble organic solvent is preferably 1 to 80 parts by mass, and more preferably 10 to 60 parts by mass, per 100 parts by mass of water.

[0104] 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 liquid-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 an amphoteric emulsifier is more preferred.

[0105] (Polymerization 2) When the polymerizable reactive group of monomers 1 to 5 is a hydrolyzable silyl group, copolymer A having units 1 to 5 is obtained by polymerizing monomers 1 to 5 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 reactions. The initiator is not limited to organic acids, inorganic acids, and Lewis acids, but can be any agent that catalyzes hydrolysis. For example, inorganic bases and organic bases may be used. For example, when the hydrolyzable silyl group is a hydrolyzable silyl group represented by formula 7, the hydrolyzable silyl group is hydrolyzed and converted to a hydroxyl group, and a siloxane bond is formed by dehydration condensation of the hydroxyl group, and polymerization proceeds.

[0106] Polymerization 2 may be carried out by the sol-gel method (Method 1), or by coating an article with a solution containing monomers 1 to 5 and then allowing polymerization to proceed using moisture in the air (Method 2).

[0107] In Method 1, it is preferable to add monomers 1 to 5 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.

[0108] In Method 2, a solution in which monomers 1 to 5 are 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, with heating being preferable. A steam-containing atmosphere is preferred for drying.

[0109] (Formation of Unit 2 after Polymerization) Unit 2 may be formed after polymerization. For example, monomer Z1, which is a precursor compound of monomer 2 and has a reactive group (Z1 group), may be used instead of monomer 2, monomer 1 and monomer Z1 may be polymerized to obtain a precursor copolymer A', and compound Z2, which has a reactive group (Z2 group) and a phosphate group that can react with the reactive group (Z1 group) in unit Z1 of precursor copolymer A', may be reacted with the reactive group (Z1 group) in unit Z1 to form unit 2.

[0110] <Liquid Media> Examples of liquid media include non-aqueous media and aqueous media. When the liquid media is a non-aqueous media, the liquid-repellent composition preferably comprises copolymer A and a non-aqueous media, and is a polymer solution in which copolymer A is dissolved or dispersed in the 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 A. When the liquid media is an aqueous media, the liquid-repellent composition preferably is a polymer dispersion containing copolymer A, an aqueous media, and an emulsifier.

[0111] (Non-aqueous medium) The non-aqueous medium is a liquid medium that does not contain water or has a water content of 1% by mass or less relative to the total mass of the non-aqueous medium, and is typically an organic solvent. The water content relative to the total mass of the non-aqueous medium is preferably 0.8% by mass or less, and more preferably 0.5% by mass or less. The non-aqueous medium is not particularly limited as long as it can dissolve copolymer A, and examples include hydrocarbon organic solvents, ketone organic solvents, alcohol organic solvents, ester organic solvents, amide organic solvents, and ether organic solvents.

[0112] Examples of hydrocarbon-based organic solvents, ketone-based organic solvents, alcohol-based organic solvents, ester-based organic solvents, and ether-based organic solvents include those similar to the organic solvents exemplified as organic solvents used in the solution polymerization method for copolymer A, and may also be water-soluble organic solvents as described later. There are no particular restrictions on amide-based organic solvents, and examples include dimethylacetamide, 3-methoxydimethylpropanamide, 3-butoxydimethylpropanamide, and methylpyrrolidone. These may be used individually or in combination of two or more.

[0113] (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 is miscible with water in any proportion. Preferably, the water-soluble organic solvent is at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols, and aprotic polar solvents. 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, acetonitrile, and acetone. When the liquid medium is an aqueous medium, ether alcohols are preferred as the water-soluble organic solvent because they improve the compatibility between copolymer A and the aqueous medium and make it easier to form a uniform film on the surface of the article, and dipropylene glycol, tripylene glycol, and dipropylene glycol monomethyl ether are more preferred. These may be used individually or in combination of two or more. When the aqueous medium contains a water-soluble organic solvent, the content of the water-soluble organic solvent is preferably 1 to 80 parts by mass, and more preferably 10 to 60 parts by mass, per 100 parts by mass of water.

[0114] <Emulsifier> The emulsifier is a surfactant having both hydrophilic and hydrophobic parts. Examples of emulsifiers include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, and amphoteric emulsifiers. Non-fluorinated emulsifiers that do not contain fluorine atoms are preferred. As for emulsifiers, from the viewpoint of excellent dispersion stability of the liquid-repellent composition, the use of a nonionic emulsifier alone, the use of a nonionic emulsifier in combination with a cationic or amphoteric emulsifier, or the use of an anionic emulsifier alone are preferred, and the use of a nonionic emulsifier in combination with an amphoteric emulsifier is more preferred. The ratio of nonionic emulsifier to amphoteric emulsifier (nonionic emulsifier / amphoteric emulsifier) ​​is preferably 100 / 0 to 40 / 60 (mass ratio), and more preferably 97 / 3 to 40 / 60 (mass ratio). In certain combinations of nonionic and amphoteric emulsifiers, the total amount of emulsifiers per 100 parts by mass of copolymer A can be reduced to 5 parts by mass or less, thereby reducing the decrease in alcohol repellency of articles using the liquid-repellent composition caused by the emulsifiers.

[0115] Examples of nonionic emulsifiers include surfactants described in paragraphs

[0067] to

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

[0116] Examples of cationic emulsifiers include surfactants described in paragraphs

[0096] to

[0100] of Japanese Patent Publication No. 2009-215370. ７ Examples include surfactants. ７ It is a substituted ammonium salt type cationic emulsifier. Surfactant s ７ Preferably, the ammonium salt is one in which one or more hydrogen atoms bonded to the nitrogen atom are substituted with an alkyl group, an alkenyl group, or a polyoxyalkylene chain having a hydroxyl group at the end, as shown in the following formula s ７１ Compounds represented by s ７１ It is more preferable. [(R ２１ ) ４ N ＋ ]・X － ...(Formula s ７１ ) R ２１ This is a polyoxyalkylene chain consisting of a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a hydroxyl group at the end. ２１ These may be the same or different, but the four R's ２１ It is not a hydrogen atom at the same time. X － X is the counterion. － Preferably, the compound is chloride ion, ethyl sulfate ion, or acetate ion. ７１ Examples include monostearyltrimethylammonium chloride, monostearyldimethylmonoethylammonium ethyl sulfate, mono(stearyl)monomethyldi(polyethylene glycol)ammonium chloride, di(tallow alkyl)dimethylammonium chloride, and dimethylmonococonutamine acetate. Cationic emulsifiers may be used individually or in combination of two or more.

[0117] Examples of amphoteric emulsifiers include surfactants described in paragraphs

[0101] to

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

[0118] <Other Components> Other components may be added to the solution or dispersion obtained by the method for producing copolymer A, or to a solution obtained by further diluting this solution or dispersion. Examples of other components include various additives for known liquid-repellent compositions, such as antistatic agents, penetrating agents, pH adjusters, flame retardants, softeners, slip-preventing agents, fray-preventing agents, wrinkle-preventing agents, stain-preventing agents, and crosslinking agents.

[0119] The liquid-repellent composition of this embodiment can achieve a reduction in surface electrical resistance even without an antistatic agent, but when an antistatic agent is included, it can provide even better antistatic properties. Examples of antistatic agents include surfactants that function as antistatic agents. Surfactants that function as antistatic agents may be anionic surfactants, nonionic surfactants, cationic surfactants, or amphoteric surfactants. Examples of anionic surfactants include phosphate ester compounds. Specifically, examples of butyl phosphate metal salts include Zelec TY (manufactured by Stepan) and AS-300 (manufactured by Mitsubishi International Polymer Trade Corporation). Examples of nonionic surfactants include polyoxyethylene compounds. Examples of cationic surfactants include alkylammonium chlorides. Examples of amphoteric surfactants include amide alkylbetaine compounds. Antistatic agents may be used individually or in combination of two or more types.

[0120] When a liquid-repellent composition contains a penetrating agent, the composition becomes more easily absorbed into hydrophobic substrates. Examples of penetrating agents include alcohols and surfactants that function as penetrating agents. The surfactant that functions as a penetrating agent may be anionic, nonionic, cationic, or amphoteric surfactants. Specific examples of penetrating agents include alcohols having an alkyl group with 1 to 10 carbon atoms (such as hexanol and octanol), polyoxyethylene alkyl ethers, and NRW-200 (manufactured by Mitsubishi International PolymerTrade Corporation), with alcohols having an alkyl group with 1 to 10 carbon atoms being preferred, and hexanol being more preferred. Penetrating agents may be used individually or in combination of two or more.

[0121] When a liquid-repellent composition contains a crosslinking agent, adhesion to the substrate 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 hydrophilic groups.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] When a liquid-repellent composition contains a methylol-based crosslinking agent or a glyoxal resin-based wrinkle-preventing agent, it is preferable to include a catalyst as an additive. Preferred catalysts include, for example, inorganic amine salts, organic amine salts, and inorganic metal salts. An example of an inorganic amine salt is ammonium chloride. Examples of organic amine salts include amino alcohol hydrochlorides and semicarbazide hydrochlorides. Examples of amino alcohol hydrochlorides include monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanolamine hydrochloride, and 2-amino-2-methylpropanol hydrochloride. An example of an inorganic metal salt is magnesium chloride.

[0126] <Proportion of each component> When the liquid repellent composition contains a liquid medium, the amount of liquid medium can be appropriately selected according to the desired solid content concentration of the liquid repellent composition. The solid content concentration of the liquid repellent composition immediately after production 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 liquid repellent composition is used for coating articles, the solid content concentration of the liquid 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. The content of copolymer A relative to the total solid content of the liquid repellent composition is preferably 10% by mass or more, more preferably 50% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The content of copolymer A relative to the total mass of the liquid 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.

[0127] When the liquid-repellent composition contains an aqueous medium, it is preferable that copolymer A is dispersed as emulsion particles in the aqueous medium. The average particle size of the emulsion particles of copolymer A is preferably 20 to 400 nm, more preferably 30 to 300 nm, and particularly preferably 50 to 250 nm. If the average particle size is below the above upper limit, film-forming properties are good, and as a result, liquid-repellent properties, especially alcohol-repellent properties, can be fully exhibited. If the average particle size is above the above lower limit, the emulsion particles are more stable against mechanical shear. The average particle size of the emulsion particles of the polymer is measured by dynamic light scattering on a sample obtained by diluting the liquid-repellent composition with water to a solid content concentration of 1% by mass.

[0128] When the liquid-repellent composition contains an emulsifier, the emulsifier content is preferably 0.01 to 5 parts by mass per 100 parts by mass of copolymer A. If the emulsifier content is below the above upper limit, the decrease in alcohol repellency of the article using the liquid-repellent composition due to the emulsifier can be reduced. If the emulsifier content is above the above lower limit, the dispersion stability of the liquid-repellent composition is further improved.

[0129] When a liquid-repellent composition contains an antistatic agent, the amount of antistatic agent is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass, relative to the total mass of the liquid-repellent composition, in order to balance the effect of the antistatic agent with water repellency and alcohol repellency. Lower antistatic agent content tends to result in superior water repellency and alcohol repellency.

[0130] When the liquid-repellent composition contains a penetrating agent, the amount of penetrating agent is preferably 0.01 to 2% by mass, and more preferably 0.1 to 1% by mass, relative to the total mass of the liquid-repellent composition, in order to achieve both penetration into hydrophobic substrates and water repellency and alcohol repellency.

[0131] The content of fluorine atoms relative to the total mass of the liquid-repellent composition is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 1% by mass or less. The liquid-repellent composition is particularly preferably a non-fluorine-based liquid-repellent composition. In other words, the content of fluorine atoms relative to the total mass of the liquid-repellent composition is particularly preferably 0.1% by mass or less, and most preferably no fluorine atoms at all. The content of fluorine atoms relative to the total mass of the liquid-repellent composition can be measured by combustion ion chromatography or the like.

[0132] The liquid-repellent composition described above contains copolymer A having unit 1 and unit 2, and can impart alcohol repellency to the substrate and reduce the surface electrical resistance. It is believed that the trialkylsilyl group of unit 1 provides the alcohol-repellent effect, and the phosphate group of unit 2 provides the effect of reducing the surface electrical resistance.

[0133] <Applications and Uses> The liquid-repellent composition of this embodiment is suitably used to impart liquid repellency to fibers (especially nonwoven fabrics), glass, paper, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded products, porous resins, porous fibrous materials, etc. From the viewpoint of alcohol repellency, the liquid-repellent composition of this disclosure is preferably for use with fibers, and more preferably for use with fibers (especially nonwoven fabrics). The liquid-repellent composition of this embodiment can be used 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, oleophobic agent, etc. It can also be used as a moisture-proof agent, water-slip agent, mold release agent, release agent, resin adhesion inhibitor, biological adhesion inhibitor, etc.

[0134] ≪Articles≫ An article according to one embodiment of the present disclosure is an article whose substrate is treated with the liquid-repellent composition of this embodiment. The article of this embodiment has a treated surface treated with the liquid-repellent composition of this embodiment. Examples of substrates (articles to be treated) to be treated with the liquid-repellent composition include fibers (textile fabrics (woven fabrics, knitted fabrics, nonwoven fabrics, napped fabrics, etc.) and 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 (including pulp), wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded articles, porous resins, and porous fibrous materials. Porous resins are used, for example, as filters. Examples of porous resin materials include polypropylene, polyethylene terephthalate, and polytetrafluoroethylene. Examples of materials for porous fibrous bodies include glass fibers, cellulose nanofibers, carbon fibers, and cellulose acetate fibers.

[0135] 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, rayon, and mixtures thereof. The thickness of the fiber fabric is not particularly limited, but is typically between 10 μm and 5 cm.

[0136] As the base material, a base material containing fibers is preferred, and from the viewpoint of water repellency and water pressure resistance, a base material containing hydrophobic fibers is preferred. Therefore, the liquid repellent composition is preferably for treating a base material containing hydrophobic fibers. Examples of hydrophobic fiber materials include polyolefins (polypropylene, polyethylene, etc.), polyvinyl chloride, nylon, polyester, and polystyrene. The base material containing hydrophobic fibers may also contain hydrophilic fibers such as cellulose fibers. Examples of forms of base materials containing hydrophobic fibers include polyolefin nonwoven fabrics (polypropylene nonwoven fabrics, polyethylene nonwoven fabrics, polypropylene and polyethylene blended nonwoven fabrics, etc.), nylon nonwoven fabrics, polyester nonwoven fabrics, and nonwoven fabrics obtained by blending these with cellulose fibers. When the article is a medical textile product, a polypropylene nonwoven fabric is preferred as the base material containing hydrophobic fibers. Therefore, the liquid repellent composition is preferably for treating polypropylene nonwoven fabrics. The liquid repellent composition is also preferably for treating nonwoven fabrics obtained by blending hydrophobic fibers and cellulose fibers.

[0137] The method for processing an article is simply to adhere the liquid-repellent composition to the article to be processed. For example, if the liquid-repellent composition contains a liquid medium, one method is to treat the article with the liquid-repellent composition by known methods such as coating, impregnation, immersion, spraying, brushing, padding, sizing press, or rolling, and then dry it. The amount of solids in the liquid-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 4 g is more preferred, and 0.1 to 3 g is even more preferred. The content of copolymer A in the liquid-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 4 g per 100 g of textile is preferred, 0.02 to 3 g is more preferred, and 0.03 to 2 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 liquid-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.

[0138] Furthermore, the substrate may be treated with an antistatic agent before being treated with the liquid-repellent composition, or the substrate may be treated with an antistatic agent after being treated with the liquid-repellent composition.

[0139] The alcohol repellency of the treated surface of the article in this embodiment is preferably grade 3 or higher, and particularly preferably grade 4 or higher. Higher alcohol repellency is preferable. Here, alcohol repellency is measured by the AATCC test method TM193 Aqueous Liquid Repellency: Water / Alcohol Solution Resistance Test, as defined by the AATCC (American Association of Textile Chemists and Colorists).

[0140] The surface electrical resistance of the treated surface of the article in this embodiment is preferably 100 GΩ or less, more preferably 80 GΩ or less, and particularly preferably 50 GΩ or less. A lower surface electrical resistance is preferable. The surface electrical resistance is measured according to Method number NWSP 040.1 of the Harmonized Nonwoven Standard Procedure jointly established by the European Disposables and Nonwovens Association and the Association of Nonwoven Fabrics Industry.

[0141] The water pressure resistance of the treated surface of the article in this embodiment is determined by increasing the pressure at a rate of 60 mbarH ２ If set to 0 / min, then 52 cm·H ２ Preferably 0 or higher, 55 cm・H ２ 0 or more is more preferable, 56 cm・H ２ A value of 0 or higher is particularly preferred. The water pressure resistance is measured according to Method number NWSP 080.6 of the Harmonized Nonwoven Standard Procedure described above.

[0142] 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, "%" means "mass%" and "parts" means "parts by mass". Examples 1 to 9 are examples, and Examples 10 to 14 are comparative examples.

[0143] <Evaluation Method> (Unit Content) The composition ratio of the polymer (the ratio of each monomer unit to the total units constituting the polymer) was calculated based on the amount of monomer component used. In each example, GPC measurements were performed on the copolymer dispersion obtained by polymerization to confirm that there were no peaks originating from monomers. Therefore, the conversion rate of each monomer component to the polymer was 90% or higher, and the ratio of each unit could be calculated based on the amount of each monomer component used.

[0144] (Evaluation of the product) Test cloths obtained by treating polypropylene nonwoven fabric with a liquid-repellent composition were evaluated for alcohol repellency, water pressure resistance (water repellency), and surface electrical resistance (antistatic properties) according to the following procedure.

[0145] [Alcohol Repellency] Evaluation was performed according to the AATCC (American Association of Textile Chemists and Colorists) test method TM193 Aqueous Liquid Repellency: Water / Alcohol Solution Resistance Test.

[0146] [Surface electrical resistance] Evaluation was performed in accordance with Method number NWSP 040.1 of the Harmonized Nonwoven Standard Procedure jointly established by the European Disposables and Nonwovens Association and the Association of Nonwoven Fabrics Industry.

[0147] [Water Pressure Resistance] The evaluation was performed according to Method number NWSP 080.6 of the Harmonized Nonwoven Standard Procedure mentioned above. The boosting speed was 60 mbarH. ２ It was set to 0 / min.

[0148] <Raw materials, etc.> (Monomer 1) m1: Compound represented by the following formula (manufactured by Tokyo Chemical Industry Co., Ltd., in formula 1 above, X 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)

[0149]

[0150] (Monomer 2) m2-1: Methacryloyloxyethyl phosphate (Unichemical product name "Hosmer M") m2-2: Methacryloyloxypolyethylene glycol phosphate (Unichemical product name "Hosmer PE") m2-3: Methacryloyloxypolypropylene glycol phosphate (Unichemical product name "Hosmer PP") (Monomer 3) VdCl: Vinylidene chloride (Monomer 4) MOI-BP: 3,5-dimethylpyrazole adduct of isocyanatoethyl methacrylate (Monomer 5) StA: Stearyl acrylate

[0151] (Chain transfer agent) DoSH: Dodecyl mercaptan (Initiator) V-50: 20% by mass aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (Fujifilm Wako Pure Chemical Industries product name "V-50") (Emulsifier) ​​E420: Polyoxyethylene oleyl ether (ethylene oxide adduct of approximately 12.8 molars, Kao Corporation product name "Emulgen 420") P204: Ethylene oxide / propylene oxide polymer (average molecular weight 3,330, containing 40% by mass of ethylene oxide, NOF Corporation product name "Pronon #204") AM-3130N: Coconut oil fatty acid amidopropyl betaine aqueous solution (Nikko Chemicals product name "NIKKOL-AM3130N")

[0152] (Liquid medium) DPG: Dipropylene glycol Water: Ion-exchanged water (Antistatic agent) Zelec TY (Stepan product name) (Penetrating agent) n-Hexanol

[0153] <Preparation of Copolymer Dispersion> (Preparation Example 1) 14.8 g of m1, 0.8 g of m2-1, 0.32 g of MOI-BP, 3.2 g of a 10% aqueous solution of E420 (active ingredient), 0.8 g of a 10% aqueous solution of P204 (active ingredient), 0.3 g of a 10% aqueous solution of AM-3130N (active ingredient), 4.8 g of DPG, and 24.1 g of water were weighed into a polypropylene container and heated to 50°C. The mixture was emulsified for 30 seconds using an ultrasonic emulsifier (BRANSON product name "Sonifier SFX550"). After keeping the resulting emulsion at 30°C, 39.3 g was placed in a glass reaction vessel, and 0.064 g of DoSH and 0.64 g of V-50 were added. The reaction vessel was gently stirred, and after confirming homogenization, the gas phase was replaced with nitrogen, the vessel was sealed, and the reaction was carried out at 60°C for 10 hours to obtain copolymer dispersion 1.

[0154] (Production Examples 2-14) Copolymer dispersions 2-14 were obtained in the same manner as in Production Example 1, except that the components and amounts used were changed as shown in Tables 1-2. However, VdCl was added after the addition of V-50 and before the gas phase was replaced with nitrogen. Although Production Example 11 is labeled as a copolymer dispersion for convenience, it is actually a dispersion of a homopolymer.

[0155]

[0156]

[0157] <Examples 1-14> A liquid-repellent composition was prepared by blending the copolymer dispersion shown in Table 3, Zelec TY, and n-hexanol to the following composition. The composition (%) is the value with the total mass of the liquid-repellent composition set to 100%. (Composition of liquid-repellent composition) Copolymer dispersion 1% (calculated as solid content concentration) Zelec TY 0.3% (product mass) n-hexanol 0.6%

[0158] Polypropylene nonwoven fabric (basis weight: 45 g / m²) ２After immersing the sample in the liquid-repellent composition for each example, the excess liquid was removed by squeezing with a rubber mangle roller. The sample was then dried in an open state at 110°C for 240 seconds to obtain the test cloth. The alcohol repellency, surface electrical resistance, and water pressure resistance (water repellency) of the test cloth were evaluated. The results are shown in Table 3. In the table, "N" indicates that the surface electrical resistance was too high and exceeded the measurement range of the device.

[0159]

[0160] In Examples 1 to 9, which used copolymers having unit 1 and unit 2, the surface electrical resistance was reduced while maintaining alcohol repellency and water pressure resistance, compared to Examples 10 to 13, which used polymers having unit 1 but not unit 2. In Example 14, which used a copolymer having units based on stearyl acrylate, which is generally considered to have liquid-repellent properties, without having either unit 1 or unit 2, the alcohol repellency was inferior to that of Examples 1 to 9, and the surface electrical resistance was also relatively high.

[0161] According to this disclosure, a liquid-repellent composition and an article using the same can be provided, which are excellent in imparting alcohol-repellent properties to a substrate and reducing surface electrical resistance. The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2025-013543, filed on January 30, 2025, are incorporated herein by reference as the disclosure of the specification of this invention.

Claims

1. A liquid-repellent composition comprising a non-fluorine copolymer having a unit based on monomer 1 represented by the following formula 1, and a unit based on monomer 2 having a polymerizable reactive group and a phosphate 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 This is a monovalent organic group having at least one trialkylsilyl group.

2. The liquid repellent composition according to claim 1, wherein the monomer 2 is a monomer represented by the following formula 2. X ２ -A ２ -B ２ ... (Formula 2) In the formula 2, X ２ is a monovalent polymerizable reactive group, A ２ is a divalent organic group, and B ２ is a phosphate group.

3. The aforementioned X １ The liquid-repellent composition according to claim 1, wherein the polymerizable reactive group of monomer 2 is independently a group having a polymerizable carbon-carbon double bond or a hydrolyzable silyl group.

4. The liquid-repellent composition according to claim 1, wherein the content of units based on monomer 1 is 50% by mass or more and 99% by mass or less relative to the total number of units constituting the non-fluorine copolymer.

5. The liquid-repellent composition according to claim 1, wherein the content of units based on the monomer 2 is 1% by mass or more and 50% by mass or less with respect to the total number of units constituting the non-fluorine copolymer.

6. The liquid-repellent composition according to claim 1, wherein the total content of units based on monomer 1 and units based on monomer 2 is 51% by mass or more and 100% by mass or less with respect to all units constituting the non-fluorine copolymer.

7. The liquid-repellent composition according to claim 1, wherein the mass ratio of the content of units based on monomer 2 to the content of units based on monomer 1 in the non-fluorine copolymer is 0.01 to 0.

50.

8. The liquid-repellent composition according to claim 1, wherein the monomer 2 is at least one selected from the group consisting of (meth)acryloyloxyalkyl phosphate, (meth)acryloyloxypolyalkylene glycol phosphate, and salts thereof.

9. The liquid-repellent composition according to claim 1, wherein the non-fluorine copolymer further comprises units based on a halogenated olefin having halogen atoms other than fluorine atoms.

10. The liquid-repellent composition according to claim 1, further comprising an antistatic agent.

11. The liquid-repellent composition according to claim 1, further comprising a penetrating agent.

12. An article obtained by treating a substrate with a liquid-repellent composition according to any one of claims 1 to 11.

13. The article according to claim 12, wherein the base material is a nonwoven fabric.

14. The article according to claim 12, which is for medical use.

15. The article according to claim 12, having a treated surface having an alcohol repellency of grade 3 or higher as measured by the AATCC test method TM193 Aqueous Liquid Repellency: Water / Alcohol Solution Resistance Test, and a surface electrical resistance of 100 GΩ or less.

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