Water and oil repellent agent composition and article

Abstract

A water and oil repellent agent composition contains a polymer having a unit based on a monomer represented by formula (1), and a compound represented by formula (3). The content of the unit based on the monomer represented by formula (1) is 20 mass% or more with respect to all units constituting the polymer. The content of the compound represented by formula (3) is from 0.1 mass% to 2.0 mass% with respect to the total mass of the polymer. Where, n1, n3, and n4 each independently represent an integer of 13-23, R1 and R5 each independently represent a hydrogen atom, a methyl group, or a halogen atom, X1, X3, and X4 each independently represent a single bond or a divalent linking group, and Y1 represents an oxygen atom or a sulfur atom.　CH2=CR1-COO-X1-(CH2)n1CH3 (1) CH3(CH2)n3-X3-Y1-CH2CHR5-COO-X4-(CH2)n4CH3 (3)

Description

Water and oil repellent composition and article

[0001] This application claims priority from Japanese Patent Application No. 2024-151725, filed on September 3, 2024, the contents of which are incorporated herein by reference.

[0002] As a method for imparting water and oil repellency to the surface of an article such as a textile product, a method of treating the article with a water and oil repellent composition containing a fluoropolymer is known. However, the fluoropolymer used in this method is concerned about its high environmental impact. Therefore, water and oil repellent compositions containing non-fluoropolymers have been studied.

[0003] As a water / oil repellent composition containing a non-fluorinated polymer, Patent Document 1 discloses a surface treatment agent that is an aqueous emulsion containing a non-fluorinated polymer having repeating units derived from a specific long-chain (meth)acrylate ester monomer, a surfactant containing a surface-active compound having both an amide group and an amino group, and a liquid medium containing water. Patent Document 2 discloses a water repellent composition containing a polymer having repeating units derived from a specific amide group-containing monomer and a liquid medium.

[0004] JP 2015-172198 A International Publication No. 2019 / 026593

[0005] However, articles treated with the water / oil repellent compositions containing the non-fluorinated polymers described in Patent Documents 1 and 2 may have insufficient slip properties. The present invention provides a water / oil repellent composition that can give articles with excellent slip properties, and an article with excellent dynamic water repellency.

[0006] The present invention has the following aspects: [1] A water / oil repellent composition comprising a polymer having units based on a monomer represented by the following formula (1) and a compound represented by the following formula (3), wherein the content of the units based on the monomer represented by (1) is 20 mass% or more relative to all units constituting the polymer, and the content of the compound represented by formula (3) is 0.1 mass% or more and 2.0 mass% or less relative to the mass of the polymer. CH ２ =CR １ -COO-X １ - (CH２ ) ｎ１ CH ３ (1) CH ３ (CH ２ ) ｎ３ -X ３ -Y １ -CH ２ CHR ５ -COO-X ４ - (CH ２ ) ｎ４ CH ３ (3) wherein n1, n3, and n4 each independently represent an integer from 13 to 23; R １ and R ５ each independently represents a hydrogen atom, a methyl group, or a halogen atom; １ , X ３ and X ４ each independently represents a single bond or a divalent linking group; Y １represents an oxygen atom or a sulfur atom. [2] The water / oil repellent composition according to [1] above, wherein the polymer further has units based on a halogenated olefin (excluding those containing fluorine atoms). [3] The water / oil repellent composition according to [1] or [2] above, wherein the polymer further has units based on a reactive monomer. [4] The water / oil repellent composition according to any of [1] to [3] above, wherein the polymer further has units based on a fluorine-containing monomer. [5] The water / oil repellent composition according to any of [1] to [3] above, wherein the polymer does not have units based on a fluorine-containing monomer, or, if it does, the content of the units based on the fluorine-containing monomer relative to all units constituting the polymer is 50 mass% or less. [6] The water / oil repellent composition according to any of [1] to [5] above, wherein the content of the compound represented by formula (3) is 0.15 mass% or more and 1.60 mass% or less relative to the mass of the polymer. [7] The water / oil repellent composition of any of [1] to [5] above, wherein the content of the compound represented by formula (3) is 0.4 mass % or more and 1.2 mass % or less relative to the total mass of the polymer. [8] The water / oil repellent composition of any of [1] to [7] above, wherein the content of units based on the monomer represented by formula (1) is 35 mass % or more relative to all units constituting the polymer. [9] The water / oil repellent composition of any of [1] to [8] above, wherein the polymer further has units based on a monomer represented by the following formula (2): CH ２ =CR ２ -COO-CH ２ CHR ３ -COO-X ２ - (CH ２ ) ｎ２ CH ３ (2) where n2 is an integer from 13 to 23, and R ２ and R ３ each independently represents a hydrogen atom, a methyl group, or a halogen atom; ２represents a single bond or a divalent linking group.

[10] The water / oil repellent composition according to any of [1] to [9] above, wherein the treated surface of an article is produced by treating a part or all of a substrate containing glass with the water / oil repellent composition, and the receding contact angle of the treated surface exceeds 85°.

[11] The water / oil repellent composition according to any of [1] to

[10] above, wherein the treated surface of an article is produced by treating a part or all of a substrate containing glass with the water / oil repellent composition, and the treated surface has a dynamic friction coefficient of 0.10 or less against artificial skin.

[12] An article treated with the water / oil repellent composition according to any of [1] to

[11] above.

[13] The article according to

[12] above, comprising a substrate and the water / oil repellent composition adhered to at least a part or all of the substrate, and the substrate comprises fibers.

[0007] According to the present invention, it is possible to provide a water / oil repellent composition that can give an article having excellent slipperiness, and an article having excellent dynamic water repellency.

[0008] The meanings and definitions of terms used in the present invention are as follows. "Monomer" refers to a compound having a polymerizable moiety such as a polymerizable unsaturated group. "Units based on a monomer" is a general term for an atomic group formed directly by polymerizing one molecule of a monomer and an atomic group obtained by chemically converting a portion of the atomic group. The content of a specific unit in a polymer is expressed as the ratio of the specific unit to the total mass of all units constituting the polymer. "(Meth)acrylate" is a general term for acrylate and methacrylate. Similarly, "(meth)acryloyl" is a general term for acryloyl and methacryloyl, and "(meth)acrylamide" is a general term for acrylamide and methacrylamide. The number average molecular weight (hereinafter also referred to as "Mn") and weight average molecular weight (hereinafter also referred to as "Mw") of a polymer are molecular weights calculated in terms of polymethyl methacrylate as measured by gel permeation chromatography (hereinafter also referred to as "GPC"). "Non-fluorinated polymer" is a general term for polymers having a fluorine atom content of 0.1% by mass or less relative to the total mass of the polymer. The fluorine atom content relative to the total mass of the polymer can be measured by combustion ion chromatography or the like. The solid content concentration is calculated by (solid content mass / sample mass) x 100, where the mass of the sample before heating is the sample mass and the mass of the sample after drying for 4 hours in a convection dryer at 120°C is the solid content mass. The symbol "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits.

[0009] [Water / Oil Repellent Composition] The water / oil repellent composition of this embodiment (hereinafter also referred to as "the composition") contains a specific polymer (hereinafter also referred to as "polymer A") and a specific compound (hereinafter also referred to as "compound B"). Polymer A has units based on a monomer (hereinafter also referred to as "monomer (a)") represented by formula (1) described below. Compound B is represented by formula (3) described below. The composition may further contain a medium. The composition may further contain a surfactant. The composition may contain other components as necessary.

[0010] <Polymer A> Polymer A has units based on monomer (a) (hereinafter also referred to as "units (a)"). Polymer A may further have one or more units selected from the group consisting of units based on monomer (b) (hereinafter also referred to as "units (b)"), units based on monomer (c) (hereinafter also referred to as "units (c)"), units based on monomer (d) (hereinafter also referred to as "units (d)"), units based on monomer (e) (hereinafter also referred to as "units (e)"), and units based on monomer (f) (hereinafter also referred to as "units (f)").

[0011] (Monomer (a)) Monomer (a) is represented by the following formula (1): CH ２ =CR １ -COO-X １ - (CH ２ ) ｎ１ CH ３ (1) where n1 represents an integer from 13 to 23, and R １ represents a hydrogen atom, a methyl group or a halogen atom, and X １ represents a single bond or a divalent linking group.

[0012] In formula (1), n1 is preferably an integer of 14 to 21. １ The halogen atom in R is preferably a halogen atom other than fluorine, and examples thereof include a chlorine atom. １ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. １ Examples of the divalent linking group in ４ -NH-CO-, -R ４ -NH-CO-O-, -R ４ In these groups, R ４ represents an alkylene group having 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms, and R ４ The end of the side is X １ bonded to the oxygen atom adjacent to

[0013] As the monomer (a), hexadecyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth)acrylate, and behenic acid amide ethyl (meth)acrylate are preferred. Two or more types of the monomer (a) may be used in combination.

[0014] (Monomer (b)) Monomer (b) is represented by the following formula (2): CH ２ =CR ２ -COO-CH ２ CHR ３ -COO-X ２ - (CH ２ ) ｎ２ CH ３ (2) where n2 is an integer from 13 to 23, and R ２ and R ３ each independently represents a hydrogen atom, a methyl group, or a halogen atom; X ２ represents a single bond or a divalent linking group. When polymer A has unit (b), the dynamic water repellency of an article treated with the present composition is improved.

[0015] In formula (2), n2 is preferably an integer of 14 to 21. ２ and R ３ The halogen atom in R is preferably a halogen atom other than fluorine, １ The halogen atoms in R ２ and R ３ are each independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. ２ As the divalent linking group in １ Examples of the divalent linking group include the same as the divalent linking group in the above formula.

[0016] Monomer (b) has a structure in which acrylic acid is added to the carbon-carbon double bond of monomer (a). In the acrylic acid, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a methyl group or a halogen atom. In formula (2), n2, R ３ , X ２ are n1 and R in formula (1), respectively. １ , X １may be the same as or different from.

[0017] Preferred examples of the monomer (b) include a compound having a structure in which (meth)acrylic acid is added to the carbon-carbon double bond of hexadecyl (meth)acrylate, a compound having a structure in which (meth)acrylic acid is added to the carbon-carbon double bond of stearyl (meth)acrylate, a compound having a structure in which (meth)acrylic acid is added to the carbon-carbon double bond of behenyl (meth)acrylate, a compound having a structure in which (meth)acrylic acid is added to the carbon-carbon double bond of palmitic acid amidoethyl (meth)acrylate, a compound having a structure in which (meth)acrylic acid is added to the carbon-carbon double bond of stearic acid amidoethyl (meth)acrylate, and a compound having a structure in which (meth)acrylic acid is added to the carbon-carbon double bond of behenic acid amidoethyl (meth)acrylate. Two or more types of monomer (b) may be used in combination.

[0018] (Monomer (c)) Monomer (c) is a halogenated olefin (excluding those containing fluorine atoms). When polymer A contains unit (c), adhesion to the article to be treated is improved, and abrasion resistance is improved. In addition, a dense water-repellent film is easily formed on the surface of the article, and initial water repellency is also improved.

[0019] Examples of halogen atoms contained in the monomer (c) include chlorine atoms, bromine atoms, and iodine atoms. Among these, chlorine atoms are preferred. When the monomer (c) has two or more halogen atoms, the two or more halogen atoms may be the same or different. As the monomer (c), a halogenated olefin having one or two halogen atoms and having two carbon atoms is preferred, and vinyl chloride and vinylidene chloride are preferred. Two or more types of monomer (c) may be used in combination.

[0020] (Monomer (d)) The monomer (d) is a reactive monomer (excluding the monomers (a), (b), (c), and the monomers (e) and (f) described below). When the polymer A has the unit (d), a reaction (e.g., a crosslinking reaction) occurs between the unit (d) and a substrate treated with the composition, and the durability of an article treated with the composition against prolonged heavy rain and against cleaning such as washing is improved.

[0021] Examples of the monomer (d) include compounds having a crosslinkable functional group and a polymerizable unsaturated group, and compounds having two or more polymerizable unsaturated groups. Examples of the polymerizable unsaturated group include groups having a carbon-carbon double bond at the molecular terminal, and preferred examples include (meth)acryloyl groups, vinyl groups, and allyl groups. Preferred crosslinkable functional groups are functional groups having at least one of a covalent bond, an ionic bond, and a hydrogen bond, or functional groups capable of forming a crosslinked structure through the interaction of the bonds. Preferred examples of the functional group include an isocyanate group, a blocked isocyanate group, an alkoxysilyl group, a primary amino group, an alkoxymethylamide group, a silanol group, a primary amide group, an epoxy group, a hydroxyl group, an oxazoline group, a carboxyl group, and a sulfonic acid group. More preferred are an isocyanate group, a blocked isocyanate group, a hydroxyl group, a primary amino group, or an epoxy group, and particularly preferred is a blocked isocyanate group.

[0022] The blocked isocyanate group is represented by the following formula (4): —N(H)—C(═O)—X ５ (4) However, X ５ represents a monovalent organic group and is a protecting group. ５ is any group capable of protecting an isocyanate group. ５ The number of carbon atoms in X is preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 6. ５ Preferably, X contains a heteroatom. Examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom and an oxygen atom are preferred. The number of heteroatoms is preferably 1 to 4, and more preferably 1 or 2. X bonded to the carbon atom in the formula (4) ５ The atom in X is preferably a heteroatom, more preferably a nitrogen atom. ５Preferred examples of X include a monovalent group obtained by removing hydrogen from the NOH group of an oxime compound, a monovalent group obtained by removing hydrogen from the NH group of a pyrazole compound, and a monovalent group obtained by removing hydrogen from the NH group of an ε-caprolactam compound. 2-Butanone oxime is preferred as the oxime compound. Preferred examples of pyrazole compounds include pyrazole and pyrazole derivatives in which the hydrogen atoms bonded to the carbon atoms in pyrazole are substituted with alkyl groups. Preferred examples of pyrazole derivatives include 3-methylpyrazole and 3,5-dimethylpyrazole. Preferred examples of ε-caprolactam compounds include ε-caprolactam and ε-caprolactam derivatives in which the hydrogen atoms bonded to the carbon atoms in ε-caprolactam are substituted with alkyl groups. X ５ is more preferably a group selected from monovalent groups obtained by removing hydrogen from an NOH group or an NH group in 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 a group selected from monovalent groups obtained by removing hydrogen from an NH group in any one compound selected from the group consisting of 3-methylpyrazole, 3,5-dimethylpyrazole, and ε-caprolactam.

[0023] As the monomer (d), (meth)acrylates having a crosslinkable functional group, (meth)acrylamides having a crosslinkable functional group, vinyl ethers having a crosslinkable functional group, or vinyl esters having a crosslinkable functional group are preferred. Examples of the monomer (d) include the following compounds.

[0024] 2-Butanone oxime adduct of 2-isocyanatoethyl (meth)acrylate (2-[0-(1'-methylpropylideneamino)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 adduct of 3-isocyanatopropyl (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, ε-caprolactam adduct of 4-isocyanatobutyl (meth)acrylate.

[0025] 2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate.

[0026] Methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, butoxymethyl (meth)acrylamide, diacetone acrylamide, γ-methacryloyloxypropyltrimethoxysilane, trimethoxyvinylsilane, and vinyltrimethoxysilane.

[0027] t-butyl(meth)acrylamidosulfonic 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, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl methacrylate, polyoxyalkylene glycol mono(meth)acrylate, (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyhexahydrophthalic acid, 2-(meth)acryloyloxyethyl acid phosphate, allyl (meth)acrylate, 2-vinyl-2-oxazoline, polycaprolactone ester of 2-vinyl-4-methyl-(2-vinyloxazoline)hydroxyethyl (meth)acrylate.

[0028] Tri(meth)allyl isocyanurate (T(M)AIC, manufactured by Nippon Kasei Chemical Co., Ltd.), triallyl cyanurate (TAC, manufactured by Nippon Kasei Chemical Co., Ltd.), 3-(methylethylketoxime)isocyanatomethyl-3,5,5-trimethylcyclohexyl(2-hydroxyethyl methacrylate) cyanate (Techcoat HE-6P, manufactured by Kyokin Chemical Co., Ltd.), and polycaprolactone ester of hydroxyethyl (meth)acrylate (Placcel FA, FM series, manufactured by Daicel Chemical Industries, Ltd.).

[0029] Preferred examples of the monomer (d) include 2-[0-(1'-methylpropylideneamino)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 (Placcel FA, FM series, manufactured by Daicel Chemical Industries, Ltd.). Two or more types of the monomer (d) may be used in combination.

[0030] (Monomer (e)) Monomer (e) is a fluorine-containing monomer. When polymer A contains unit (e), the water- and oil-repellency of an article treated with the composition is improved. In addition, a coating liquid for forming a moisture-permeable waterproof layer may be applied to one side of a fabric treated with the composition and cured to form a moisture-permeable waterproof layer having fine pores. In such a case, when polymer A contains unit (e), excessive penetration of the coating liquid into the fibers of the fabric can be suppressed. If the coating liquid excessively penetrates into the fibers and leaks from one side of the fabric to which the coating liquid is applied to the other, moisture-permeable waterproof layers will be formed on both sides of the fabric, causing whitening of the surface of the fabric and impairing the design and texture. From the perspective of environmental impact, polymer A may not contain unit (e). In particular, even if the present composition does not contain units (e), it can exhibit sufficient water and oil repellency, particularly dynamic water repellency and slipperiness, as a water and oil repellent composition containing a non-fluorinated polymer.

[0031] Examples of the monomer (e) include polyfluoroalkyl groups (hereinafter referred to as "R ｆ Examples of the monomer include a monomer having a fluorine atom, and a halogenated olefin containing a fluorine atom.

[0032] R ｆ In the monomer having the group R ｆ From the viewpoint of environmental load, the number of carbon atoms in the group is preferably 1 to 6, and more preferably 1 to 4. ｆ The monomer having a group may be a monomer having a polyfluoropolyether group. ｆ Examples of the monomer having a group include (Z-Q) ｎ Examples of the compound represented by X include:

[0033] Z is R having 1 to 6 carbon atoms. ｆ group or C ｊ F ２ｊ＋１ O (CFX １１ CF ２ O) ｋ CFX １２ -, j represents an integer of 1 to 6, k represents an integer of 0 to 10, and X １１ and X １２R each independently represents a fluorine atom or a trifluoromethyl group. ｆ The group includes a perfluoroalkyl group (hereinafter referred to as "R Ｆ R is preferably a substituted or unsubstituted alkyl group. ｆ The group may be linear or branched, and is preferably linear. Z is, for example, F(CF ２ ) ４ -, F(CF ２ ) ５ -, F(CF ２ ) ６ -, (CF ３ ) ２ CF (CF ２ ) ２ -, C ｊ F ２ｊ＋１ O[CF(CF ３ )CF ２ O] ｋ CF (CF ３ )- are listed.

[0034] Q represents a divalent organic group or a single bond. ｎ In the compound represented by X, the boundary between Z and Q is determined so that Z has the fewest carbon atoms. The divalent organic group is preferably an alkylene group or an alkenylene group, more preferably an alkylene group. The alkylene group may be linear or branched. The alkylene group may have -O-, -NH-, -CO-, -S-, or -SO between carbon atoms or at the terminal on the side bonding to Z. ２ -, -CX １３ =CX １４ - (However, X １３ and X １４ each independently represents a hydrogen atom or a methyl group.

[0035] Q is, for example, —CH ２ -, -CH ２ CH ２ -, -(CH ２ ) ３ -, -CH ２ CH ２ CH (CH ３ )-,-CH=CH-CH ２ -, -S-CH ２ CH２ -, -CH ２ CH ２ -S-CH ２ CH ２ -, -CH ２ CH ２ -SO ２ -CH ２ CH ２ -, -X １５ -OC(O)NH-A-NHC(O)O-(C ｐ H2 ｐ where p is an integer of 2 to 30, A is an unbranched symmetrical alkylene group, arylene group, or aralkylene group, and X １５ is -SO ２ NX １６ -C ｄ H ２ｄ --, --CONHC ｄ H ２ｄ -, -CH(R Ｆ１ )-C ｅ H ２ｅ -or-C ｑ H ２ｑ Indicates -. X １６ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, d represents an integer of 2 to 8, and R Ｆ１ is R having 1 to 20 carbon atoms Ｆ group, e represents an integer of 0 to 6, and q represents an integer of 1 to 20. Ｆ１ R having 1 to 6 carbon atoms Ｆ R groups having 1 to 4 carbon atoms are preferred. Ｆ The group is more preferred.

[0036] n represents 1 or 2. When n is 1, X represents -CR=CH ２ , -C(O)OCR=CH ２ , -OC(O)CR=CH ２ , -OCH ２ -φ-CR=CH ２ or -OCH=CH ２ When n is 2, it is a group represented by -CH[-(CH ２ ) ｍ CR=CH ２ ]-,-CH[-(CH ２ ) ｍ C(O)OCR=CH ２]-,-CH[-(CH ２ ) ｍ OC(O)CR=CH ２ ]- or -OC(O)CH=CHC(O)O-, where R is a hydrogen atom, a methyl group, or a halogen atom, φ is a phenylene group, and m is an integer of 0 to 4.

[0037] R ｆ As the monomer having a group, a monomer having an R group having 1 to 6 carbon atoms is preferred from the viewpoints of polymerizability with other monomers, flexibility of a film containing polymer A, adhesiveness of polymer A to an article, dispersibility in a medium, ease of emulsion polymerization, etc. Ｆ From the viewpoint of environmental load, an olefin or (meth)acrylate having an R group having 1 to 4 carbon atoms is preferred. Ｆ More preferred are olefins or (meth)acrylates having a group (Z-Q). ｎ A compound represented by X, wherein Z is R Ｆ group, Q is an alkylene group having 1 to 4 carbon atoms, n is 1, and X is -CR=CH ２ or -C(O)OCR=CH ２ and Z is R Ｆ group, Q is an alkylene group having 1 to 4 carbon atoms, n is 1, and X is -CR=CH ２ or -C(O)OCR=CH ２ More preferred is a compound in which:

[0038] Examples of the halogenated olefin containing a fluorine atom include tetrafluoroethylene, vinylidene fluoride, and chlorotrifluoroethylene. Two or more types of monomer (e) may be used in combination.

[0039] (Monomer (f)) Monomer (f) is a monomer other than monomer (a), monomer (b), monomer (c), monomer (d) and monomer (e). The monomer (f) may be any monomer as long as it is copolymerizable with monomer (a), monomer (b) or the like, and examples thereof include methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylate having a polydimethylsiloxane group, styrene and vinyl acetate. Two or more types of monomer (f) may be used in combination.

[0040] The content of units (a) in polymer A is 20% by mass or more, preferably 20 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 60 to 100% by mass, particularly preferably 70 to 99% by mass, and most preferably 80 to 90% by mass, based on the total units constituting polymer A. The content of units (a) may be, for example, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more. The content of units (a) is preferably 25% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, particularly preferably 40% by mass or more, most preferably 55% by mass or more, and may even be 100% by mass. When the content of units (a) is equal to or greater than the above-mentioned lower limit, the water and oil repellency of articles treated with this composition is excellent. When polymer A has units other than unit (a), the content of unit (a) is preferably 99.9% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less, based on all units constituting polymer A. When the content of unit (a) is equal to or less than the above upper limit, the effects of units other than unit (a) are easily obtained. The above lower limit and upper limit can be appropriately combined.

[0041] When polymer A contains unit (b), the content of unit (b) is preferably 0.08 to 2 mass%, more preferably 0.10 to 1.9 mass%, more preferably 0.10 to 1.8 mass%, and even more preferably 0.90 to 1.8 mass%, based on all units constituting polymer A. When the content of unit (b) is equal to or greater than the above-mentioned lower limit, the dynamic water repellency of an article treated with the present composition is superior. When the content of unit (b) is equal to or less than the above-mentioned upper limit, the polymerization stability during polymerization of the monomer components forming polymer A is superior.

[0042] When polymer A contains units (c), the content of units (c) is preferably 5 to 30 mass%, more preferably 8 to 25 mass%, and even more preferably 10 to 20 mass%, based on all units constituting polymer A. When the content of units (c) is equal to or greater than the above-mentioned lower limit, the abrasion resistance and initial water repellency of an article treated with the present composition are superior. When the content of units (c) is equal to or less than the above-mentioned upper limit, discoloration of an article treated with the present composition is suppressed.

[0043] When polymer A contains units (d), the content of units (d) is preferably 0.5 to 10 mass%, more preferably 0.8 to 8 mass%, and even more preferably 1 to 5 mass%, based on all units constituting polymer A. When the content of units (d) is at least the above-mentioned lower limit, articles treated with the composition have better durability against prolonged heavy rain and better durability when washed by laundry or the like. When the content of units (d) is at most the above-mentioned upper limit, articles treated with the composition have better flexibility.

[0044] When polymer A contains units (e), the content of units (e) may be, for example, 50% by mass or less, 40% by mass or less, 30% by mass or less, or 20% by mass or less, relative to all units constituting polymer A. The content of units (e) is preferably 5 to 50% by mass, more preferably 8 to 40% by mass, and even more preferably 10 to 35% by mass. When the content of units (e) is equal to or greater than the above-mentioned lower limit, articles treated with the composition exhibit superior water and oil repellency and superior permeation suppression effect of coating liquids for forming moisture-permeable waterproof layers. From the viewpoint of environmental impact, it is preferable that the content of units (e) is equal to or less than the above-mentioned upper limit. Even with a small amount of units (e), which are fluorine-containing monomers, articles treated with the composition can exhibit sufficient water and oil repellency, particularly dynamic water repellency.

[0045] When polymer A contains unit (f), the content of unit (f) can be appropriately selected depending on the purpose of using unit (f) and is not particularly limited. For example, the content of unit (f) is preferably 1 to 30 mass%, more preferably 5 to 25 mass%, and even more preferably 10 to 20 mass%, based on all units constituting polymer A. The total content of unit (a), unit (b), unit (c), unit (d), unit (e), and unit (f) does not exceed 100 mass% based on all units constituting polymer A.

[0046] The ratio of each unit is: １ It can be calculated from the reaction rate of each monomer component by H-NMR, gas chromatography, and high performance liquid chromatography. When the conversion rate of the monomer components to Polymer A is high (for example, 90% or more) during the production of Polymer A, the proportion of each unit may be calculated based on the amount of the monomer components charged.

[0047] Polymer A is preferably a non-fluorine-containing polymer. Polymer A exhibits excellent water repellency even if it does not contain fluorine atoms, because it contains the units (a) in the above-mentioned specific ratio.

[0048] The Mn of polymer A is preferably 5,000 to 200,000, more preferably 8,000 to 150,000, and even more preferably 10,000 to 100,000. When the Mn of polymer A is equal to or greater than the above-mentioned lower limit, the water- and oil-repellency of an article treated with the composition and its durability when washed, for example, by laundry are superior. When the Mn of polymer A is equal to or less than the above-mentioned upper limit, the polymerization stability when polymerizing the monomer components that form polymer A is superior. The Mw of polymer A is preferably 10,000 to 1,000,000, more preferably 20,000 to 800,000, and even more preferably 30,000 to 600,000. When the Mw of polymer A is equal to or greater than the above-mentioned lower limit, the water- and oil-repellency of an article treated with the composition and its durability when washed, for example, by laundry are superior. When the Mw of polymer A is equal to or less than the upper limit, the polymerization stability is better when polymerizing the monomer components that form polymer A. Polymer A preferably satisfies at least one of the above-mentioned Mn range and the above-mentioned Mw range, and more preferably satisfies both of them.

[0049] Polymer A can be produced, for example, by the following method. A method of polymerizing a monomer component containing monomer (a) in the presence of a polymerization initiator and a polymerization medium to obtain a solution or dispersion of polymer A. The monomer component may further contain one or more monomers selected from the group consisting of monomer (b), monomer (c), monomer (d), monomer (e), and monomer (f), as necessary. When polymerizing the monomer component, a molecular weight modifier, surfactant, or dispersant may be present, as necessary. When polymerizing the monomer component, compound B may be present.

[0050] The content ratio of each monomer contained in the monomer component is the same as the content ratio of the units based on each monomer described above, since almost no remaining monomer is detected after polymerization, and the preferred embodiments are also the same. For each monomer, a commercially available product can be used. Monomers produced by known methods may also be used. An example of a method for producing monomer (a) is a method for producing a monomer by the reaction of acrylic acid chloride and HO-X ２ - (CH ２ ) ｎ２ CH ３An example of a method for producing the monomer (b) is a method for reacting an acrylic acid dimer with an alcohol represented by the formula: ２ - (CH ２ ) ｎ２ CH ３ An example of such a method is to react the compound with an alcohol represented by the formula:

[0051] The polymerization method may be solution polymerization, dispersion polymerization, emulsion polymerization, or suspension polymerization. It may be batch polymerization, continuous polymerization, or multi-stage polymerization. The polymerization temperature is preferably 20 to 150°C.

[0052] Preferred methods for producing polymer A include solution polymerization of monomer components in a polymerization medium comprising an organic solvent in the presence of a polymerization initiator to obtain a solution of polymer A, or emulsion polymerization of monomer components in an aqueous polymerization medium in the presence of a surfactant and a polymerization initiator to obtain an emulsion of polymer A. When obtaining an emulsion of polymer A by emulsion polymerization, it is preferred to pre-emulsify a mixture of monomer components, surfactant, and aqueous polymerization medium prior to emulsion polymerization, in order to improve the yield of polymer A. Examples of pre-emulsification methods include mixing and dispersing a mixture of monomer components, surfactant, and aqueous polymerization medium using a homomixer or a high-pressure emulsifier.

[0053] Examples of polymerization media include water, alcohols, glycols, glycol ethers, glycol esters, halogenated compounds, hydrocarbons, ketones, esters, ethers, nitrogen compounds, sulfur compounds, inorganic solvents, organic acids, and fluorine-based solvents. Specific examples of these media include the same media as those described in paragraphs

[0057] to

[0063] of JP 2009-215370 A. In the case of emulsion polymerization, one or more polymerization media selected from the group consisting of water, alcohols, glycols, glycol ethers, and glycol esters are preferred. In the case of solution polymerization, one or more polymerization media selected from the group consisting of hydrocarbons, ethers, fluorine-based solvents, ketones, and alcohols are preferred, and a polymerization medium containing at least a hydrocarbon is more preferred. Two or more polymerization media may be used in combination.

[0054] Examples of the polymerization initiator include a thermal polymerization initiator, a photopolymerization initiator, a radiation polymerization initiator, a radical polymerization initiator, and an ionic polymerization initiator, with a water-soluble or oil-soluble radical polymerization initiator being preferred. As the radical polymerization initiator, a general-purpose initiator such as an azo polymerization initiator, a peroxide polymerization initiator, or a redox initiator is used depending on the polymerization temperature. Among these, an azo compound is preferred, and when polymerization is performed in an aqueous medium, a salt of an azo compound is more preferred. The amount of the polymerization initiator added is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the monomer component.

[0055] When polymerizing the monomer components, a molecular weight modifier may be used. As the molecular weight modifier, an aromatic compound, a mercapto alcohol, a mercaptocarboxylic acid, or a mercaptan is preferable, and a mercaptocarboxylic acid or an alkyl mercaptan is more preferable. As the molecular weight modifier, mercaptoethanol, mercaptopropionic acid, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, stearyl mercaptan, α-methylstyrene dimer (CH ２ =C(Ph)CH ２ C(CH ３ ) ２ Ph) is a phenyl group. The amount of the molecular weight modifier added is preferably 0 to 5 parts by mass, more preferably 0 to 2 parts by mass, per 100 parts by mass of the monomer component.

[0056] The content of polymer A in the composition is preferably 10% by mass or more, more preferably 15% by mass or more, relative to the total mass of the composition, and is preferably 50% by mass or less, more preferably 40% by mass or less, relative to the total mass of the composition.

[0057] <Compound B> Compound B is represented by the following formula (3): CH ３ (CH ２ ) ｎ３ -X ３ -Y １ -CH ２ CHR ５ -COO-X ４ - (CH ２ ) ｎ４ CH３ (3) where n3 and n4 each independently represent an integer from 13 to 23, and R ５ represents a hydrogen atom, a methyl group or a halogen atom; X ３ and X ４ each independently represents a single bond or a divalent linking group; Y １ represents an oxygen atom or a sulfur atom.

[0058] In formula (3), n3 and n4 are each independently preferably an integer of 14 to 21. n3 and n4 may be the same or different. ５ The halogen atom in R １ The halogen atoms in R ５ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. ３ and X ４ As the divalent linking group in １ Examples of the divalent linking group include the same as the divalent linking group in the above formula.

[0059] Compound B is a monomer (a) having an alcohol or thiol (CH ３ (CH ２ ) ｎ３ -X ３ -Y １ In formula (3), n4, R ５ , X ４ are n1 and R in formula (1), respectively. １ , X １ may be the same as or different from.

[0060] Preferred examples of compound B include a compound having a structure in which hexahexadecanol is added to the carbon-carbon double bond of hexadecyl (meth)acrylate, a compound having a structure in which stearyl alcohol is added to the carbon-carbon double bond of stearyl (meth)acrylate, a compound having a structure in which behenyl alcohol is added to the carbon-carbon double bond of behenyl (meth)acrylate, a compound having a structure in which palmitic acid monoethanolamide is added to the carbon-carbon double bond of palmitic acid amidoethyl (meth)acrylate, a compound having a structure in which stearic acid monoethanolamide is added to the carbon-carbon double bond of stearic acid amidoethyl (meth)acrylate, and a compound having a structure in which behenic acid monoethanolamide is added to the carbon-carbon double bond of behenic acid amidoethyl (meth)acrylate. Two or more types of compound B may be used in combination. Compound B may be, for example, a monomer (a) and a CH ３ (CH ２ ) ｎ３ -X ３ -Y １ It can be produced by reacting an alcohol or thiol represented by —H with the compound in the presence of an acid catalyst such as paratoluenesulfonic acid.

[0061] The content of compound B is 0.1 to 2.0 mass%, preferably 0.15 to 1.60 mass%, more preferably 0.15 to 0.30 mass% or 0.4 to 1.55 mass%, and even more preferably 0.15 to 0.30 mass% or 0.4 to 1.2 mass%, relative to the total mass of polymer A. When the content of compound B is equal to or greater than the above-mentioned lower limit, articles treated with the composition exhibit excellent slip properties and water repellency and friction durability. Furthermore, when the article is used for mold release purposes, the releasability is also excellent. When the content of compound B is equal to or less than the above-mentioned upper limit, excellent polymerization stability is achieved when the monomer components that form polymer A are polymerized in the presence of compound B.

[0062] <Medium> Examples of the medium include the same medium as the polymerization medium described above. Two or more types of medium may be used in combination. It is preferable that the polymerization medium used in the polymerization of polymer A is contained as the medium of the composition of the present invention. In this case, the composition may further contain a medium different from the polymerization medium used in the polymerization. When the composition contains two or more types of medium, it is easy to control the solubility or dispersibility of polymer A, and it is easy to control the permeability, wettability, solvent drying rate, etc. of the composition to the substrate during processing. When polymer A is obtained by emulsion polymerization, it is preferable that the composition contains water as the medium. When polymer A is obtained by solution polymerization, it is preferable that the composition contains a hydrocarbon as the medium. The content of the medium can be appropriately selected depending on the desired solids concentration of the composition.

[0063] <Surfactants> Examples of surfactants include hydrocarbon surfactants and fluorine surfactants. For each of the hydrocarbon surfactants and fluorine surfactants, examples include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Preferred surfactants are those that do not contain fluorine atoms. From the viewpoint of dispersion stability, preferred surfactants are a combination of a nonionic surfactant and a cationic surfactant or an amphoteric surfactant, or an anionic surfactant alone, and more preferred are a combination of a nonionic surfactant and a cationic surfactant. The mass ratio of the nonionic surfactant to the cationic surfactant is preferably 97 / 3 to 40 / 60. In certain combinations of a nonionic surfactant and a cationic surfactant, the total amount relative to polymer A (100% by mass) can be 5% by mass or less, thereby reducing adverse effects on the water repellency of the article.

[0064] Examples of the nonionic surfactant include surfactants described in paragraphs

[0067] to

[0095] of JP-A-2009-215370. １ ~s ６ These may be used alone or in combination of two or more. １is a polyoxyalkylene monoalkyl ether, a polyoxyalkylene monoalkenyl ether, a polyoxyalkylene monoalkapolyenyl ether, or a polyoxyalkylene monopolyfluoroalkyl ether. １ As the surfactant, for example, polyoxyethylene oleyl ether is preferred. ２ is a nonionic surfactant consisting of a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in the molecule. ２ As the surfactant, for example, an acetylene glycol ethylene oxide adduct is preferred. ３ is a nonionic surfactant consisting of a compound in which a polyoxyethylene chain is linked to a polyoxyalkylene chain in which two or more oxyalkylene units each having three or more carbon atoms are linked in succession, and both ends of the polyoxyalkylene chain are hydroxyl groups. ３ As the polymer, for example, ethylene oxide propylene oxide polymer is preferred.

[0065] Examples of cationic surfactants include surfactants described in paragraphs

[0096] to

[0100] of JP-A-2009-215370. ７ These may be used alone or in combination of two or more. ７ is a cationic surfactant in the form of a substituted ammonium salt. ７ As the ammonium salt, an ammonium salt 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 is preferred, and the ammonium salt represented by the following formula s ７１ More preferred is a compound represented by [(R ２１ ) ４ N ＋ ]・X － ...Formula s ７１ However, R ２１ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a polyoxyalkylene chain having a terminal hydroxyl group. ２１ may be the same or different, but four R２１ is not a hydrogen atom at the same time. － is a counter ion. － As the cation, a chloride ion, an ethyl sulfate ion, or an acetate ion is preferred. ７１ Examples of the compound represented by the formula (I) include monostearyl trimethyl ammonium chloride, monostearyl dimethyl monoethyl ammonium ethyl sulfate, mono(stearyl) monomethyl di(polyethylene glycol) ammonium chloride, monofluorohexyl trimethyl ammonium chloride, di(tallow alkyl) dimethyl ammonium chloride, and dimethyl monococonut amine acetate.

[0066] Examples of amphoteric surfactants include surfactants described in paragraphs

[0101] to

[0102] of JP-A-2009-215370. ８ Surfactants include: ８ is alanine, imidazolinium betaine, amido betaine or acetic acid betaine. These may be used alone or in combination of two or more.

[0067] In addition, surfactants described in paragraphs

[0103] to

[0107] of JP-A-2009-215370 ９ Surfactants such as: ９ are polymer surfactants consisting of block copolymers, random copolymers, or hydrophobically modified hydrophilic copolymers of a hydrophilic monomer and either or both of a hydrocarbon-based hydrophobic monomer and a fluorine-based hydrophobic monomer. These may be used alone or in combination of two or more.

[0068] As for the combination of surfactants, surfactants s and s are preferred in terms of the water repellency and durability of the article treated with the composition and the stability of the resulting emulsion. １ and surfactants ２ and surfactants ７ or a combination of surfactants １ and surfactants ３ and surfactants ７ or a combination of surfactants １ and surfactants ２ and surfactants３ and surfactants ７ The combination of surfactant s is preferred. ７ is the formula s ７１ The above combination is more preferably a compound represented by the formula:

[0069] When the composition contains a surfactant, the content of the surfactant is preferably 1 to 6 parts by mass per 100 parts by mass of polymer A. When the content of the surfactant is equal to or greater than the lower limit, the dispersion stability of the composition is excellent. When the content of the surfactant is equal to or less than the upper limit, adverse effects of the surfactant on the water and oil repellency of an article treated with the composition can be reduced.

[0070] <Other Components> Examples of other components include polymers or resins other than Polymer A (for example, acrylic polymers other than Polymer A, urethane polymers), water / oil repellent compositions or water / oil repellents other than the present composition, water-soluble polymer resins (for example, hydrophilic polyesters and derivatives thereof, hydrophilic polyethylene glycols and derivatives thereof, hydrophilic polyamines and derivatives thereof, hydrophilic polyvinyl alcohols and derivatives thereof), crosslinking agents, penetrating agents (for example, nonionic surfactants with a symmetrical structure having an acetylene group in the center, Dispanol (registered trademark) series manufactured by NOF Corporation), colloidal silica (for example, Snowtex (registered trademark) silica manufactured by Nissan Chemical Industries, Ltd.), and the like. Examples of such additives include: ADEKA Adelite series, antifoaming agents (e.g., Nissin Chemical Industry Co., Ltd.'s Olfin (registered trademark) series, and Toray Dow Corning Co., Ltd.'s FS Antifoam series), film-forming aids, insect repellents, mildew inhibitors, preservatives, flame retardants, antistatic agents (e.g., Meisei Chemical Industry Co., Ltd.'s Directol series), anti-wrinkle agents, softeners (e.g., silicone emulsions, polyethylene wax emulsions, polyamide wax emulsions), pH adjusters (e.g., diethanolamine, triethanolamine, acetic acid, citric acid), and fatty acid amides (e.g., those described in JP 2014-98082 A). Two or more of these may be used in combination.

[0071] When the composition contains a crosslinking agent as an additive, adhesion to the substrate is likely to be improved. The crosslinking agent is preferably at least one selected from the group consisting of isocyanate-based crosslinking agents, melamine-based crosslinking agents, carbodiimide-based crosslinking agents, and oxazoline-based crosslinking agents. Specific examples of isocyanate-based crosslinking agents include aromatic block-type isocyanate-based crosslinking agents, aliphatic block-type isocyanate-based crosslinking agents, aromatic unblock-type isocyanate-based crosslinking agents, and aliphatic unblock-type isocyanate-based crosslinking agents. When processed in an aqueous medium, these isocyanate-based crosslinking agents are preferably water-dispersible agents emulsified with a surfactant or self-dispersible agents containing hydrophilic groups. Specific examples of melamine-based crosslinking agents include condensates or pre-condensates of urea or melamine formaldehyde, methylol-dihydroxyethylene-urea and its derivatives, uron, methylol-ethylene-urea, methylol-propylene-urea, methylol-triazone, dicyandiamide-formaldehyde condensates, methylol-carbamate, methylol-(meth)acrylamide, and polymers thereof. Carbodiimide-based crosslinking agents are polymers having carbodiimide groups in the molecule and exhibit excellent reactivity with carboxy groups, amino groups, or active hydrogen groups in the substrate or the present composition. Oxazoline-based crosslinking agents are polymers having oxazoline groups in the molecule and exhibit excellent reactivity with carboxy groups in the substrate or the present composition. Other crosslinking agents include divinyl sulfone, polyamide and its cationic derivatives, polyamine and its cationic derivatives, epoxy derivatives such as diglycidyl glycerol, 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-epichlorohydrin resins, polyvinyl alcohol and its derivatives, polyacrylamide and its derivatives, and glyoxal resin-based wrinkle inhibitors.

[0072] When the present composition contains a melamine-based crosslinking agent or a glyoxal resin-based wrinkle-resistant agent, it is preferable to include a catalyst as an additive. Preferred catalysts include inorganic amine salts and organic amine salts. Examples of inorganic amine salts include ammonium chloride. Examples of organic amine salts include amino alcohol hydrochlorides and semicarbazide hydrochloride. Examples of amino alcohol hydrochlorides include monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanolamine hydrochloride, and 2-amino-2-methylpropanol hydrochloride.

[0073] <Method for preparing water / oil repellent composition> The solution or dispersion of polymer A obtained by the method for producing polymer A may be used as a water / oil repellent composition as is. In this case, polymer A is produced in the presence of compound B. The water / oil repellent composition may be prepared by adjusting the solids concentration by diluting a solution of polymer A containing compound B with the above-mentioned medium. The water / oil repellent composition may also be prepared by adding one or more components selected from the group consisting of compound B, surfactants, and other components to a solution of polymer A.

[0074] The solids concentration of the composition is not particularly limited as long as polymer A and compound B are stably dissolved or dispersed. The solids concentration of the composition immediately after production is preferably 0.1 to 50 mass%, more preferably 0.2 to 40 mass%, and even more preferably 10 to 40 mass%, relative to the total mass of the composition. When the composition is used to treat a substrate, the solids concentration of the composition is preferably 0.1 to 10 mass%, more preferably 0.2 to 5 mass%, and even more preferably 0.5 to 3 mass%, relative to the total mass of the composition.

[0075] <Mechanism of Action> The composition described above contains polymer A having unit (a) and compound B, and the content of unit (a) is 20% by mass or more relative to all units constituting polymer A, and the content of compound B is 0.1 to 2.0% by mass relative to the total mass of polymer A, so that an article having excellent slip properties and dynamic water repellency can be obtained. When the article is used for mold release purposes, it also has excellent mold releasability. It is believed that the presence of compound B, a long-chain hydrocarbon compound containing ether groups and ester groups, results in excellent crystallinity and a low coefficient of dynamic friction on the surface.

[0076] [Article] The article of the present embodiment (hereinafter also referred to as "the article") is an article treated with the composition of the present invention. The article preferably includes a substrate, a polymer A, and a compound B, and the polymer A and the compound B are present in a state of being adhered to the substrate.

[0077] Examples of substrates include fibers, glass, paper, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded products, porous resins, and porous fibers. Paper or fibers are preferred, and fibers are more preferred. Examples of fibers include fiber fabrics (woven fiber fabrics, knitted fiber fabrics, nonwoven fabrics, and raised fabrics), fiber products containing fiber fabrics (skiwear, rainwear, coats, blousons, windbreakers, down jackets, sportswear, work clothes, uniforms, protective clothing, and other clothing, backpacks, bags, tents, and tarps), and porous fibers. The type of fiber is not particularly limited, but examples include natural fibers such as cotton, wool, silk, and cellulose; synthetic fibers such as polyester, polyamide, acrylic, and aramid; chemical fibers such as rayon, viscose rayon, and lyocell; blended fibers of natural fibers and synthetic fibers; and blended fibers of natural fibers and chemical fibers. When the fiber fabric is a nonwoven fabric, examples of the fibers include polyethylene, polypropylene, polyolefin, polyethylene terephthalate, polytetrafluoroethylene, glass, and rayon. The thickness of the fiber fabric is not particularly limited, but is usually 0.01 to 5 mm. Examples of the porous resin material include polypropylene, polyethylene terephthalate, and polytetrafluoroethylene.

[0078] The present article can be obtained by treating a substrate with the present composition. For example, the present article can be produced by applying the present composition to at least a portion or all of a substrate. The method for applying the present composition to a substrate is not particularly limited. For example, when the present composition contains a medium, the composition can be applied to the surface of the substrate by a coating process such as coating, impregnation, immersion, spraying, brushing, padding, size press, or roller, followed by drying. Drying can be performed at room temperature or by heating, but heating is preferred. When heating, heating to approximately 40 to 200°C is preferred. Furthermore, when the present composition contains a crosslinking agent, curing is preferably performed by heating to a temperature equal to or higher than the crosslinking temperature of the crosslinking agent.

[0079] When the substrate is a fiber, a moisture-permeable waterproof layer may be formed by contacting a coating liquid for forming a moisture-permeable waterproof layer with the surface of the fiber treated with the present composition (hereinafter also referred to as the "treated surface"). An article having a moisture-permeable waterproof layer formed on the treated surface is suitable for textile products that require waterproofness and moisture permeability.

[0080] The coating liquid may be a known one, for example, a liquid composition containing a coating resin and a solvent. Examples of coating resins include polyurethane resins obtained by reacting a polyisocyanate component with a polyol component, polycarbonate copolymer polyurethane resins, polyurethane resins copolymerized with silicone, fluorine, amino acids, etc., acrylic resins, polyester resins, polyether copolymers, synthetic rubbers, vinyl resins such as polyvinyl chloride, and polytetrafluoroethylene resins. Two or more coating resins may be used in combination. Examples of solvents include toluene, methyl ethyl ketone, N,N-dimethylformamide (hereinafter referred to as "DMF"), N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, and hexamethylene phosphonamide. Polar organic solvents are preferred as the solvent. The liquid composition may further contain an auxiliary agent. Examples of auxiliary agents include fluorine-based water repellents and crosslinking agents.

[0081] The method for contacting the coating liquid with the treatment surface is not particularly limited, and known methods can be used. Examples include a method of applying the coating liquid to the treatment surface using a spatula or brush, or a method of uniformly applying the coating liquid to the treatment surface using a knife coater, knife-over-roll coater, blade coater, reverse roll coater, spin coater, or kiss roll. After applying the coating liquid to the treatment surface using these known methods, the coating is left to stand for a predetermined period of time, followed by heat drying or immersion in water to form a moisture-permeable waterproof layer. When a highly volatile, low-water-soluble solvent such as toluene or methyl ethyl ketone is used as the coating liquid solvent, heat drying is preferred. Heat drying evaporates the coating resin in the coating liquid, forming a coating film and forming a porous moisture-permeable waterproof layer with numerous micropores in the coating film, thereby enabling moisture-permeable waterproofing. When a polar organic solvent such as DMF, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, or hexamethylene phosphonamide is used as the coating liquid solvent, water immersion is preferred. By immersing in water, the coating resin in the coating liquid forms a film, and the polar organic solvent in the coating liquid migrates to the aqueous phase, forming numerous micropores in the film, forming a porous moisture-permeable waterproof layer and enabling moisture-permeable waterproofing. The size of the pores in the moisture-permeable waterproof layer is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 0.1 to 3 μm, to improve the moisture-permeable waterproofing function. The size of the pores in the moisture-permeable waterproof layer can be measured using a scanning electron microscope. The lower limit of 0.1 μm means that the size of the pores visible with a scanning electron microscope is 0.1 μm or more, and it is believed that smaller pores exist.

[0082] When the present article is an article produced by treating a part or all of a substrate containing glass with the present composition, the receding contact angle of water on the treated surface of the present article is preferably greater than 85°C, more preferably 88°C or higher, and even more preferably 90°C or higher. The method for measuring the receding contact angle is as described in the Examples below. When the present article is an article produced by treating a part or all of a substrate containing glass with the present composition, the dynamic friction coefficient of the treated surface of the present article against artificial skin is preferably 0.10 or less, more preferably 0.08 or less, and even more preferably 0.06 or less. The method for measuring the dynamic friction coefficient is as described in the Examples below.

[0083] [Applications and Uses] This embodiment includes the use of a composition containing the above-described polymer A as a water / oil repellent. This embodiment also includes a water / oil repellent composition for paper or fibers (preferably fibers) containing the above-described polymer A, and the use of a composition containing the above-described polymer A as a water / oil repellent composition for paper or fibers (preferably fibers).

[0084] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the description of the following examples. Examples 1, 3, 5, 7, 9, 10 to 13, and 16 to 17 are working examples, and Examples 2, 4, 6, 8, 14 to 15, and 18 are comparative examples.

[0085] <Proportion of Monomer Units> The composition of the polymer (proportion of each monomer unit to all units constituting the polymer) was calculated based on the amount of the monomer component charged. The solution or dispersion obtained by polymerization in each example was subjected to GPC measurement to confirm the absence of peaks derived from the monomer. Therefore, the conversion rate of each monomer component to the polymer was 90% or more, and the proportion of each unit could be calculated based on the amount of each monomer component charged.

[0086] <Molecular Weight of Polymer> The polymers obtained by polymerization in each example were subjected to GPC measurement, and it was confirmed that the number average molecular weight of all polymers except for Example 5 was within the range of 50,000 to 80,000 and the weight average molecular weight was within the range of 120,000 to 180,000.

[0087] <Evaluation of Polymerization Stability> When the polymerized monomer components were polymerized, if the obtained polymer did not become a homogeneous liquid and floating matter or foreign matter was present, it was rated as "B", and otherwise it was rated as "A". An evaluation of "A" indicates excellent polymerization stability.

[0088] <Evaluation of Test Glass Plate> (Receding Contact Angle) The receding contact angle of water on the surface of the test glass plate was measured using a Dataphysics surface tensiometer (DCAT11). 200 mL of pure water was used, and the water temperature was 20°C ± 0.2°C. A receding contact angle of water greater than 85°, preferably 90° or greater, indicates excellent dynamic water repellency.

[0089] (Dynamic Friction Coefficient) The dynamic friction coefficient of the surface of the test glass plate against artificial skin (PBZ13001, manufactured by Idemitsu Technofine Co., Ltd.) was measured using a load-varying friction and wear testing system (HHS2000, manufactured by Shinto Scientific Co., Ltd.) under conditions of a contact area of ​​3 cm × 3 cm and a load of 0.98 N. When the dynamic friction coefficient is 0.10 or less, preferably 0.08 or less, and more preferably 0.06 or less, the slip properties and releasability are excellent.

[0090] <Evaluation of Test Cloth> (Initial Water Repellency) The water repellency of the test cloth was evaluated according to the spray test of JIS L 1092:1998, using a five-level scale of 1 to 5. The higher the scale, the better the water repellency. A scale with a + next to it indicates that the water repellency is slightly better than the standard level for that scale. A scale with a - next to it indicates that the water repellency is slightly worse than the standard level for that scale. A scale of 4 or higher, preferably 4+ or higher, indicates excellent initial water repellency.

[0091] (Tape peelability) A 25 mm long polyester tape (manufactured by Nitto Denko Corporation) was attached to a test fabric, and a 2 kg pressure roller was rolled back and forth twice on the tape. The substrate with the polyester tape attached was set in a tensile tester, and the peel strength was measured under measurement conditions of a speed of 300 mm / min, a grip width of 25 mm, and a peel distance of 50 mm, and the tape peelability was evaluated according to the following criteria. An evaluation result of A indicates excellent tape peelability. A: Peel strength less than 0.50 N. B: Peel strength 0.50 N or more.

[0092] (Water repellency (dry friction)) The test cloth for which the water repellency (initial) evaluation was performed was subjected to 2,000 friction cycles on the friction surface of the test cloth using a friction tester, and the test cloth was air-dried overnight in a room at a temperature of 25°C and a humidity of 55%, after which the water repellency was evaluated, and the water repellency after dry friction was evaluated according to the following criteria. An evaluation result of A indicates excellent water repellency (dry friction). A: The decrease from the water repellency (initial) is less than grade 1. B: The decrease from the water repellency (initial) is grade 1 or more.

[0093] <Abbreviation> (Monomer (a)) StA: stearyl acrylate BeA: behenyl acrylate StAeA: stearic acid amide ethyl acrylate (Monomer (b)) StAA: a compound having a structure in which acrylic acid is added to the carbon-carbon double bond of StA (R in formula (2) ２ and R ３ H, X ２ is a single bond, and n2 is 17) (Monomer (c)) VCM: vinyl chloride VdCl: vinylidene chloride (Monomer (d)) HEMA: 2-hydroxyethyl methacrylate HEA: 2-hydroxyethyl acrylate NMAM: N-methylolacrylamide MOIBP: 2-(3,5-dimethylpyrazolyl)carbonylaminoethyl methacrylate (Monomer (e)) C6FMA: CH ２ =C(CH ３ )-COO-(CH ２ ) ２ -(CF ２ ) ６ F C1FMA:CH ２ =C(CH ３ )-COO-CH ２ -CF ３

[0094] (Compound B) StA-StOH: A compound having a structure in which stearyl alcohol (StOH) is added to the carbon-carbon double bond of StA (R in formula (3) ５ H, X ３ and X ４ is a single bond, Y １ is an oxygen atom, and n3 and n4 are 17) BeA-BeOH: a compound in which behenyl alcohol (BeOH) is added to the carbon-carbon double bond of BeA (R in formula (3)５ H, X ３ and X ４ is a single bond, Y １ is an oxygen atom, and n3 and n4 are 21) StAeA-StAEOH: a compound in which stearic acid monoethanolamide (StAEOH) is added to the carbon-carbon double bond of StAeA (R in formula (3) ５ H, X ３ and X ４ Ga-(CH ２ ) ２ -NH-CO-, Y １ is an oxygen atom, and n3 and n4 are 16)

[0095] (Molecular weight modifier) ​​StSH: stearyl mercaptan (Polymerization initiator) VA061A: 20% by mass aqueous solution of 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (VA-061, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) acetate (VA-061:acetic acid = 1:0.8 (mass ratio)) V65: 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) (Surfactant) E420: polyoxyethylene oleyl ether (approximately 12.8 mol ethylene oxide adduct, Kao Corporation product name Emulgen 420) P204: ethylene oxide-propylene oxide polymer (average molecular weight 3,330, contains 40% by mass ethylene oxide, NOF Corporation product name Pronon #204) AQ18: 63% by mass solution of alkyl chloride (carbon number: 16 to 18) trimethylammonium chloride in water and isopropyl alcohol (trade name: Lipocard 18-63, Lion Specialty Chemicals) SFY485: Acetylene glycol ethylene oxide adduct (ethylene oxide addition mole number: 30 moles, Nissin Chemical Industry Co., Ltd. trade name: Surfynol 485) (medium) DPG: Dipropylene glycol Water: Ion-exchanged water, toluene

[0096] Production Example 1: Synthesis of StA StA was obtained by reacting stearyl alcohol (StOH) with acrylic acid chloride. Specifically, 10 g of stearyl alcohol, triethylamine (1.2 molar equivalents relative to the amount of stearyl alcohol), and 20 mL of toluene were added to a reactor (capacity: 50 mL, made of glass) equipped with a stirrer and a dropping funnel and stirred. Subsequently, the internal temperature of the reactor was adjusted to 10° C. or less in an ice bath, and acrylic acid chloride (1.1 molar equivalents relative to the amount of stearyl alcohol) was added dropwise under a nitrogen atmosphere. The mixture was then returned to room temperature and stirred for 2 hours. The resulting crude reaction liquid was washed three times with 30 mL of distilled water using a separatory funnel, and the solvent in the toluene layer was distilled off to obtain StA.

[0097] <Production Example 2: Synthesis of BeA> BeA was obtained in the same manner as in Production Example 1, except that behenyl alcohol (BeOH) was used instead of StOH.

[0098] <Production Example 3: Synthesis of StAeA> StAeA was obtained in the same manner as in Production Example 1, except that stearic acid monoethanolamide (StAEOH) was used instead of StOH.

[0099] <Production Example 4: Synthesis of StAA> StAA was obtained by reacting StOH with chloride of acrylic acid dimer. Specifically, 50 g of acrylic acid dimer (manufactured by Sigma-Aldrich Co.) and 50 mg of paramethoxyphenol were added to a reactor (capacity: 100 mL, made of glass) equipped with a stirrer, a reflux condenser, and a dropping funnel, and the mixture was stirred. Phosphorus trichloride (0.32 molar equivalents relative to the acrylic acid dimer) was added dropwise at an internal temperature of 55°C over 120 minutes. After stirring for 90 minutes, DMF (0.06 molar equivalents relative to the acrylic acid dimer) was added dropwise at an internal temperature of 30°C over 50 minutes. After stirring for 30 minutes, 2.0 mg of paramethoxyphenol was added. The mixture was distilled at a temperature of 70°C and a reduced pressure of 40 Torr to obtain chloride of acrylic acid dimer. Thereafter, StAA was obtained in the same manner as in Production Example 1.

[0100] Production Example 5: Synthesis of StA-StOH StOH and StA were reacted in the presence of paratoluenesulfonic acid (PTSA) to obtain StA-StOH. Specifically, 10 g of StA obtained in Production Example 1, 8.3 g of StOH (the same molar equivalent as StA), 0.27 g of PTSA (0.05 molar equivalent as StA), 50 mg of paramethoxyphenol, and 20 mL of toluene were placed in a reactor (capacity: 50 mL, made of glass) equipped with a stirrer, and the mixture was stirred at 60°C for 4 hours. The resulting crude reaction liquid was washed three times with 30 mL of distilled water using a separatory funnel, and the solvent in the toluene layer was evaporated to obtain StA-StOH.

[0101] Production Example 6: Synthesis of BeA-BeOH BeA-BeOH was obtained in the same manner as in Production Example 4, except that BeOH was used instead of StOH and BeA was used instead of StA.

[0102] Production Example 7: Synthesis of StAeA-StAEOH StAeA-StAEOH was obtained in the same manner as in Production Example 4, except that StAEOH was used instead of StOH and StAeA was used instead of StA.

[0103] <Examples 1 to 6> A stainless steel reactor was charged with the monomer, compound B, polymerization initiator, and medium shown in Table 1, and polymerization was carried out at 60°C for 12 hours while shaking under a nitrogen atmosphere to obtain a solution containing a polymer. In Table 1, the unit of the blending amount of each component is parts by mass. The evaluation results of polymerization stability in each example are shown in Table 1. In Example 6, solidification was observed, so the subsequent operations were not carried out.

[0104] The resulting dispersion was diluted with tetrahydrofuran to a solids concentration of 2% by mass to prepare a treatment liquid. A test glass plate was prepared using the resulting treatment liquid. Specifically, 15 g of the treatment liquid was heated to 50°C, and a glass plate serving as a substrate was immersed in the treatment liquid three times, followed by a curing heat treatment at 150°C for 10 minutes to prepare a test glass plate. The receding contact angle and dynamic friction coefficient with respect to water were measured for the resulting test glass plate. The results are shown in Table 1.

[0105]

[0106] Examples 1, 3, and 5 were superior in dynamic water repellency to Examples 2 and 4, and also had smaller dynamic friction coefficients and superior slip properties. One possible reason for this is that Examples 1, 3, and 5 contained Compound B. Example 6 had poor polymerization stability. One possible reason for this is that the content of Compound B exceeded 2.0% by mass relative to the total mass of the polymer.

[0107] Examples 7 to 9: The monomers (excluding monomer (c)), compound B, surfactants (where AQ18 indicates the amount of active ingredient), molecular weight modifier, and medium shown in Table 2 were placed in a glass container and heated at 60°C for 60 minutes. The mixture was then mixed using a homomixer (Biomixer, manufactured by Nippon Seiki Seisakusho Co., Ltd.) to obtain a mixed solution. While maintaining the temperature at 60°C, the mixed solution was pre-emulsified at 10 MPa using a high-pressure emulsifier (Minilab, manufactured by APV Lanier) and then treated at 40 MPa to obtain an emulsion. The resulting emulsion was placed in a stainless steel reactor and cooled to below 30°C. A polymerization initiator shown in Table 2 was added thereto, and the gas phase was replaced with nitrogen. Then, monomer (c) shown in Table 2 was introduced and polymerized at 60°C for 10 hours with stirring to obtain a polymer-containing dispersion. None of the resulting dispersions contained any suspended matter or foreign matter, and were rated "A" in the polymerization stability evaluation. In Table 2, the amount of each component is expressed in parts by mass.

[0108] The resulting dispersion was diluted with ion-exchanged water to a solids concentration of 1% by mass to prepare a treatment solution. A test cloth was prepared using the resulting treatment solution. Specifically, dyed nylon taffeta was immersed in the treatment solution by padding and squeezed to a wet pickup of 60% by mass. This was dried at 110°C for 90 seconds and then further dried at 180°C for 60 seconds to prepare a test cloth. The water repellency (initial) and tape peelability of the resulting test cloth were evaluated. The results are shown in Table 2. For Examples 7 and 9, test glass plates were prepared in the same manner as in Examples 1 to 6, and the receding contact angle and dynamic friction coefficient with water were measured. The receding contact angle was greater than 85° and the dynamic friction coefficient was 0.10 or less.

[0109]

[0110] Examples 7 and 9 were superior in water repellency (initial) and tape peelability to Example 8. The reason for this is thought to be, for example, that Examples 7 and 9 contained Compound B.

[0111] Examples 10 to 18 Monomers (excluding monomer (c)), compound B, surfactants (where AQ18 indicates the amount of active ingredient), molecular weight modifiers, and media shown in Tables 3 and 4 were placed in a glass autoclave and heated at 60°C for 60 minutes. The mixture was then mixed using a homomixer (Biomixer, manufactured by Nippon Seiki Seisakusho Co., Ltd.) to obtain a mixture. While maintaining the mixture at 60°C, the mixture was pre-emulsified at 10 MPa using a high-pressure emulsifier (Minilab, manufactured by APV Lanier) and then treated at 40 MPa to obtain an emulsion. The resulting emulsion was placed in a stainless steel reactor and cooled to below 30°C. A polymerization initiator shown in Tables 3 and 4 was added thereto, and the gas phase was replaced with nitrogen. Then, monomers (c) shown in Tables 3 and 4 were introduced and polymerized at 60°C for 10 hours with stirring to obtain a dispersion containing a polymer. None of the resulting dispersions contained any suspended matter or foreign matter, and they were rated as "A" in the polymerization stability evaluation. In Tables 3 and 4, the amount of each component is expressed in parts by mass.

[0112] The resulting dispersion was diluted with ion-exchanged water to a solids concentration of 1.2% by mass, and an isocyanate-based crosslinking agent (Meisei Chemical Industry Co., Ltd., product name: Meikanate CX) was added to a concentration of 1.0% by mass to prepare a treatment solution. Test cloths were prepared using the resulting treatment solution. Specifically, dyed nylon taffeta was immersed in the treatment solution by padding and squeezed to a wet pickup of 60% by mass. This was dried at 110°C for 90 seconds and then further dried at 180°C for 60 seconds to prepare a test cloth. The water repellency (dry friction) of the resulting test cloths was evaluated. The results are shown in Tables 3 and 4. For Examples 10 to 13 and Examples 16 to 17, test glass plates were prepared in the same manner as in Examples 1 to 6, and the receding contact angle and dynamic friction coefficient with water were measured. It was confirmed that the receding contact angle was greater than 85° and the dynamic friction coefficient was 0.10 or less.

[0113]

[0114]

[0115] Examples 10 to 13 were superior in water repellency (dry friction) to Examples 14 and 15. Similarly, Examples 16 and 17 were superior in water repellency (dry friction) to Example 18. One possible reason for this is that Examples 10 to 13 and Examples 16 to 17 contained Compound B, for example.

Claims

1. A water / oil repellent composition comprising a polymer having units based on a monomer represented by the following formula (1) and a compound represented by the following formula (3), wherein the content of the units based on the monomer represented by (1) is 20 mass% or more relative to all units constituting the polymer, and the content of the compound represented by formula (3) is 0.1 mass% or more and 2.0 mass% or less relative to the total mass of the polymer. CH ２ =CR １ -COO-X １ - (CH ２ ) ｎ１ CH ３ (1) CH ３ (CH ２ ) ｎ３ -X ３ -Y １ -CH ２ CHR ５ -COO-X ４ - (CH ２ ) ｎ４ CH ３ (3) wherein n1, n3, and n4 each independently represent an integer from 13 to 23; R １ and R ５ each independently represents a hydrogen atom, a methyl group, or a halogen atom; １ , X ３ and X ４ each independently represents a single bond or a divalent linking group; Y １ represents an oxygen atom or a sulfur atom.

2. The water / oil repellent composition according to claim 1, wherein the polymer further comprises units based on a halogenated olefin (excluding those containing fluorine atoms).

3. The water / oil repellent composition according to claim 1, wherein the polymer further comprises units derived from a reactive monomer.

4. The water / oil repellent composition according to claim 1, wherein the polymer further comprises units based on a fluorine-containing monomer.

5. The water / oil repellent composition according to claim 1, wherein the polymer does not contain any units based on a fluorine-containing monomer, or if it does contain any units based on a fluorine-containing monomer, the content of such units based on a fluorine-containing monomer relative to all units constituting the polymer is 50 mass% or less.

6. The water / oil repellent composition according to claim 1, wherein the content of the compound represented by formula (3) is 0.15% by mass or more and 1.60% by mass or less relative to the mass of the polymer.

7. The water / oil repellent composition according to claim 1, wherein the content of the compound represented by formula (3) is 0.4 mass % or more and 1.2 mass % or less relative to the mass of the polymer.

8. A water / oil repellent composition according to claim 1, wherein the content of units based on the monomer represented by formula (1) is 35 mass% or more based on all units constituting the polymer.

9. The water / oil repellent composition according to claim 1, wherein the polymer further comprises a unit based on a monomer represented by the following formula (2): CH ２ =CR ２ -COO-CH ２ CHR ３ -COO-X ２ - (CH ２ ) ｎ２ CH ３ (2) where n2 is an integer from 13 to 23, and R ２ and R ３ each independently represents a hydrogen atom, a methyl group, or a halogen atom; ２ represents a single bond or a divalent linking group.

10. The water / oil repellent composition according to claim 1, wherein the receding contact angle of the treated surface of an article produced by treating part or all of a substrate containing glass with the water / oil repellent composition is greater than 85°.

11. The water / oil repellent composition according to claim 1, wherein the treated surface of an article produced by treating a portion or all of a substrate containing glass with the water / oil repellent composition has a dynamic friction coefficient against artificial skin of 0.10 or less.

12. An article treated with the water and oil repellent composition according to any one of claims 1 to 11.

13. The article according to claim 12, comprising a substrate and the water / oil repellent composition adhered to at least a portion or all of the substrate, the substrate comprising a fiber.

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