Liquid-repellent composition, method for treating substrate, and article

Abstract

The present invention provides: a liquid-repellent agent composition which can impart excellent liquid repellency in spite of the fact that the composition is based on a hydrocarbon; a method for treating a substrate using the liquid-repellent agent composition; and an article provided with a coating film that has excellent liquid repellency in spite of the fact that the coating film is based on a hydrocarbon.　The liquid-repellent agent composition according to the present invention contains a polymer (A) having a unit based on a monomer (a); the method for treating a substrate according to the present invention includes treating the substrate with the liquid-repellent agent composition according to the present invention; and the article according to the present invention is provided with a substrate treated with the liquid-repellent agent composition according to the present invention.　Formula A: (R1-Q1―)HC=CH(-Q2―R2) Q1 and Q2 independently represent a bivalent linking group. R1 and R2 independently represent a monovalent hydrocarbon group having 8 to 24 carbon atoms.

Description

[Technical Field]

[0001] The present invention relates to a liquid-repellent composition, a method for treating a substrate, and articles. [Background technology]

[0002] Fluorine-based liquid repellents containing fluorine compounds can impart liquid repellency to the surface of an article. This is because the surface tension of the article treated with the fluorine-based liquid repellent decreases due to the fluorine in the fluorine compound, resulting in liquid repellency. For example, fluorine-based liquid repellents containing polymers with perfluoroalkyl groups as the fluorine compound are used in various fields.

[0003] In recent years, non-fluorinated water repellents have been proposed in consideration of energy conservation, cost reduction, and stricter regulations on long-chain fluoroalkyl compounds such as perfluorooctanoic acid (PFOA). Patent documents 1 to 3 disclose hydrocarbon-based water repellents containing non-fluorinated polymers having long-chain alkyl (meth)acrylate units as non-fluorinated water repellents. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2006-328624 [Patent Document 2] Japanese Patent Publication No. 2015-172198 [Patent Document 3] Japanese Patent Publication No. 2017-025440 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, the water-repellent agents described in Patent Documents 1 to 3 do not provide sufficient liquid repellency. The present invention provides a liquor repellent composition that can impart excellent liquor repellency despite being hydrocarbon-based; a method for treating a substrate using the liquor repellent composition; and an article having a coating film that exhibits excellent liquor repellency despite being hydrocarbon-based.

Means for Solving the Problem

[0006] The present invention has the following aspects. [1] A liquid repellent composition comprising a polymer (A) having a unit derived from a monomer (a) represented by the following formula (a). (R 1 -Q 1 ―)HC=CH(-Q 2 ―R 2 ) Formula (a) In formula (a), Q 1 and Q 2 each independently represent a divalent linking group, R 1 and R 2 each independently represent a monovalent hydrocarbon group having 8 to 24 carbon atoms. [2] The liquid repellent composition according to [1], wherein Q 1 and Q 2 of the monomer (a) are each independently -C(=O)-, -C(=O)-O-, -O-C(=O)-, or -C(=O)-NH-. [3] The liquid repellent composition according to [1] or [2], wherein R 1 and R 2 of the monomer (a) are each independently a monovalent hydrocarbon group having 12 to 24 carbon atoms. [4] The liquid repellent composition according to any one of [1] to [3], wherein the polymer (A) is a copolymer further having a unit derived from the following monomer (b). Monomer (b): a monomer other than the monomer (a), which has one polymerizable unsaturated group per molecule and an electron-donating group adjacent to the unsaturated group. [5] The liquid repellent composition according to [4], wherein the monomer (b) is a monomer (b1) represented by the following formula (b1). CH2=CHR 3 ···Formula (b1) In formula (b1), R 3 is an electron-donating group. [6] The electron-donating group is an optionally substituted aliphatic hydrocarbon group, -O-C(=O)-R 4 , -O-R4 , and -NH-C(=O)-R 4 A liquid repellent composition according to [5], which is at least one selected from the group consisting of the following. Here, R 4 This represents an aliphatic hydrocarbon group which may have substituents. [7] The liquid repellent composition according to any one of [4] to [6], wherein the proportion of units based on the monomer (a) is 5 to 80% by mass with respect to the total constituent units of the polymer (A). [8] The liquid repellent composition according to any one of [4] to [7], wherein the proportion of units based on monomer (b) is 20 to 95% by mass with respect to all constituent units of polymer (A). [9] The liquid-repellent composition according to any one of [1] to [5], wherein the polymer (A) is a copolymer further having units based on monomer (c) represented by the following formula (c). CH2=CX 1 X 2 ...Formula (c) In formula (c), X 1 , X 2 Each of these independently represents either a halogen atom or a hydrogen atom, and X 1 and X 2 It is not a hydrogen atom at the same time.

[10] The liquid repellent composition according to [9], wherein the monomer (c) is at least one selected from the group consisting of vinyl chloride and vinylidene chloride.

[11] The liquid repellent composition according to any one of [1] to

[10] , wherein the polymer (A) is a copolymer further having units based on monomer (d) represented by the following formula (d). CH2=CR 5 C(=O)OR 6 ...Formula (d) In formula (d), R 5 R represents a hydrogen atom or a methyl group. 6 This represents a monovalent hydrocarbon group which may have substituents.

[12] The liquid repellent composition according to any one of [1] to

[11] , wherein the polymer (A) is a copolymer further having units based on a monomer (e) having a crosslinkable functional group.

[13] A liquid repellent composition according to any one of [1] to

[12] , wherein the polymer (A) does not contain fluorine atoms. A method for treating a substrate, comprising treating the substrate with a liquid-repellent composition described in any of

[14] [1] to

[13] . An article having a substrate treated with any of the liquid-repellent compositions described in

[15] [1] to

[13] . [Effects of the Invention]

[0007] The present invention provides a hydrophobic composition that can impart excellent hydrophobicity despite being hydrocarbon-based; a method for treating a substrate using the hydrophobic composition; and an article having a coating film that exhibits excellent hydrophobicity despite being hydrocarbon-based. [Modes for carrying out the invention]

[0008] In this specification, the monomer represented by formula (a) will also be referred to as monomer (a). Other monomers represented by other formulas will be referred to similarly. In this specification, the compound represented by formula (1) will also be referred to as compound (1). The same applies to compounds represented by other formulas. The meanings and definitions of terms used in this invention are as follows: "Liquid repellency" refers to either water repellency or oil repellency, or both. A "monomer-based unit" is a general term for atomic groups that are directly formed by the polymerization of one monomer molecule, and atomic groups that are obtained by chemically transforming a part of that atomic group. "(Meth)acrylate" is a general term for acrylates and methacrylates. The number-average molecular weight (Mn) and mass-average molecular weight (Mw) of the polymer are polystyrene-equivalent molecular weights obtained by GPC measurement using a calibration curve prepared with standard polymethyl methacrylate samples. GPC stands for gel permeation chromatography. The "solids content concentration" is calculated by (solids content / sample mass) × 100, where the sample mass is the mass of the sample before heating, and the solids content mass is the mass of the sample after drying it in a convection dryer at 120°C for 4 hours. In chemical formulas, "pH" represents the phenyl group. The "~" symbol indicating a numerical range means that the numbers before and after it are included as the lower and upper limits, respectively. The content and numerical ranges of various physical properties disclosed herein can be modified by arbitrarily combining their lower and upper limits to create new numerical ranges.

[0009] [Liquid-repellent composition] The liquid-repellent composition of the present invention (hereinafter also referred to as "this composition") contains polymer (A). This composition may contain polymer (A) alone, or it may contain two or more polymers (A).

[0010] (Polymer (A)) Polymer (A) has units based on monomer (a) (hereinafter also referred to as "unit (a)"). (R 1 -Q 1 ―)HC=CH(-Q 2 ―R 2 ) Formula (a)

[0011] In formula (a), R 1 and R 2 Each of these independently represents a monovalent hydrocarbon group with 8 to 24 carbon atoms. 1 and R 2 They may be the same or they may be different. R 1 and R 2 In this case, the monovalent hydrocarbon group has 8 or more carbon atoms, resulting in excellent liquid repellency. 1 and R 2 In this case, the number of carbon atoms in the monovalent hydrocarbon group is 24 or less, resulting in excellent film-forming properties for polymer (A).

[0012] R 1 and R 2 Each of these is independently preferably a monovalent hydrocarbon group having 12 to 24 carbon atoms, more preferably a monovalent hydrocarbon group having 12 to 22 carbon atoms, and even more preferably a monovalent hydrocarbon group having 14 to 20 carbon atoms.

[0013] A monovalent aliphatic hydrocarbon group is preferred as the monovalent hydrocarbon group. The monovalent aliphatic hydrocarbon group may be linear or branched. Furthermore, the monovalent aliphatic hydrocarbon group may be saturated or unsaturated hydrocarbon group. A monovalent saturated hydrocarbon group, i.e., an alkyl group, is preferred as the monovalent aliphatic hydrocarbon group, and a linear alkyl group is more preferred. Examples of monovalent hydrocarbon groups include the lauryl group, myristyl group, cetyl group, stearyl group, arachidyl group, behenyl group, 2-ethylhexyl group, isostearyl group, and oleyl group.

[0014] In formula (a), Q 1 and Q 2 Each of these independently represents a divalent linking group. Q 1 and Q 2 They may be the same or they may be different. Q 1 and Q 2 It is preferable that they be the same. Q 1 and Q 2 From the viewpoint of the polymerizability of monomer (a), it is preferable that it has a carbonyl group (-C(=O)-). For example, Q 1 and Q 2 It is more preferable that each of these be independently -C(=O)-, -C(=O)-O-, -OC(=O)-, or -C(=O)-NH-.

[0015] From the viewpoint of superior liquid-repellent properties, monomer (a1), monomer (a2), monomer (a3), and monomer (a4) are preferred as monomer (a), with monomer (a2) being more preferred. R 1 -C(=O)-CH=CH-C(=O)-R 2 Formula (a1) R 1 -OC(=O)-CH=CH-C(=O)-OR 2 Formula (a2) R 1 -NH-C(=O)-CH=CH-C(=O)-NH-R 2 Formula (a3) R 1 -C(=O)-O-CH=CH-OC(=O)-R2 Formula (a4) In each equation, there are two R 1 , R 2 They may be the same or different. Also, R 1 and R 2 The details and preferred embodiments are the same as those described for formula (a).

[0016] Examples of monomers (a1) include trans-diastearoylethylene, cis-diastearoylethylene, trans-dilaurylethylene, cis-dilaurylethylene, trans-stearoyllauroylethylene, and cis-stearoyllauroylethylene. Examples of monomers (a2) include distearyl fumarate, distearyl maleate, diisostearyl fumarate, diisostearyl maleate, dilauryl fumarate, dilauryl maleate, di-2-ethylhexyl fumarate, di-2-ethylhexyl maleate, stearyl-2-ethylhexyl maleate, stearyl-2-ethylhexyl fumarate, stearyl lauryl maleate, and stearyl lauryl fumarate. Examples of monomers (a3) ​​include distearyl fumarate, distearyl maleate, diisostearyl fumarate, diisostearyl maleate, di-2-ethylhexyl fumarate, stearyl-2-ethylhexyl fumarate, and stearyl-2-ethylhexyl maleate. Examples of monomers (a4) include vinylenedisteadyrate, vinylenedisteadyrate, vinylene-2-ethylhexanoate, vinylenediisostearate, vinylenestearate-laurylate, and vinylenedisteadyrate-2-ethylhexanoate.

[0017] Monomers (a1), (a2), (a3), and (a4) may be commercially available or synthesized. Furthermore, each of these monomers may be used individually or in combination of two or more.

[0018] Monomer (a1) can be produced, for example, by alkylation reaction of a maleic acid ester, maleic acid amide, fumaric acid ester, or fumaric acid amide with an organomagnesium reagent having an alkyl group with 8 to 24 carbon atoms.

[0019] Monomer (a2) can be produced, for example, by reacting compound (1) with one or both of compound (2) and compound (3) in a total of 2 moles for 1 mole of compound (1) (esterification reaction). Y 1 -C(=O)-CH=CH-C(=O)-Y 2 Formula (1) R 1 -OH formula (2) R 2 -OH formula (3) However, Y 1 and Y 2 Each of these independently represents either a chlorine atom or a hydroxyl group. The esterification reaction can be carried out, for example, by the method described in paragraphs 0053 and 0054 of Japanese Patent Publication No. 2009-84490. After the esterification reaction, the reactants may be purified as needed.

[0020] Monomer (a3) ​​can be produced, for example, by the amidation reaction of maleic acid or fumaric acid with an amine having an alkyl group with 8 to 24 carbon atoms.

[0021] Monomer (a4) can be produced, for example, by an esterification reaction of glyoxal with an acid chloride having an alkyl group with 8 to 24 carbon atoms.

[0022] Polymer (A) may also be a copolymer having units based on monomer (b) described below (hereinafter also referred to as "unit (b)"). Monomer (b): A monomer other than monomer (a), which has one polymerizable unsaturated group and an electron-donating group adjacent to the unsaturated group in one molecule.

[0023] Monomer (b) has one polymerizable unsaturated group and an electron-donating group adjacent to the unsaturated group in one molecule, and therefore exhibits excellent polymerization reactivity. When monomer (b) is used in the polymerization reaction of polymer (A), the polymerization reaction of monomer (a), which has relatively low polymerizability, proceeds more easily.

[0024] Monomer (b) is not particularly limited as long as it can copolymerize with monomer (a). As monomer (b), a non-fluorinated monomer that does not contain fluorine atoms is preferred. When polymer (A) contains unit (b), if unit (b) is a unit based on a non-fluorinated monomer, polymer (A) is more likely to be a non-fluorinated polymer.

[0025] The monomer (b1) described below is preferred as monomer (b). CH2=CHR 3 ...Formula (b1) In formula (b1), R 3 It is an electron-donating group.

[0026] In formula (b1), R 3 The electron-donating group is not particularly limited as long as it is a group that can donate electrons to the unsaturated double bond of the monomer (b1). 3 Examples of electron-donating groups include heteroatom-containing groups in which a heteroatom is bonded to a carbon atom having a double bond, aliphatic hydrocarbon groups which may have substituents, and aromatic hydrocarbon groups which may have substituents.

[0027] Examples of heteroatoms in the heteroatom-containing group include oxygen, nitrogen, phosphorus, sulfur, silicon, and boron atoms. Among these, oxygen and nitrogen atoms are preferred due to their availability. When the heteroatom is an oxygen atom, examples of electron-donating heteroatom-containing groups include ether groups and ester groups. When the heteroatom is a nitrogen atom, examples of electron-donating heteroatom-containing groups include amide bonds and amine groups.

[0028] Examples of aliphatic hydrocarbon groups that may have substituents include alkyl groups and substituted alkyl groups. The number of carbon atoms in the alkyl group is not particularly limited. For example, the number of carbon atoms in the alkyl group may be 1 to 30, 3 to 24, or 4 to 20. Furthermore, the aliphatic hydrocarbon group may be linear or branched. In alkyl groups with substituents, it is sufficient that at least one methylene unit is bonded to the carbon atom having the double bond shown in formula (b1), and the position of the substituent is not particularly limited. Furthermore, the substituent itself is not particularly limited. Examples of substituents include hydroxyl groups, ether groups, carboxyl groups, amino groups, and amide groups.

[0029] Examples of substituents in an aromatic hydrocarbon group that may have substituents include a phenyl group, a styrene group, a pyridine group, a substituted phenyl group, a substituted styrene group, and a substituted pyridine group. In an aromatic hydrocarbon group with substituents, it is sufficient that at least one methylene unit or phenyl group is bonded to the carbon atom having the double bond shown in formula (b1), and the position of the substituent is not particularly limited. Furthermore, the substituent is not particularly limited. Examples of substituents include a hydroxyl group, a carboxyl group, and an ether group.

[0030] R 3 When is a heteroatom-containing group, examples of monomers (b1) include vinyl esters, vinyl ethers, amides, and silanes. Examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl chloroacetate, divinyl adipate, vinyl trifluoroacetate, vinyl benzoate, and vinyl 2-ethylhexanoate. Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, 4-hydroxybutyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether, chloromethyl vinyl ether, 2-chloroethyl vinyl ether, chloropropyl vinyl ether, cyclohexyl vinyl ether, diethylene glycol divinyl ether, ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether. Examples of amides include N-vinylacetamide, 1-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, and N-vinylphthalimide. Examples of silanes include trimethylvinylsilane, dimethylphenylvinylsilane, and diphenylmethylvinylsilane.

[0031] R 3 When is an aliphatic hydrocarbon group which may have substituents, an example of monomer (b1) is an α-olefin which may have substituents. Examples of α-olefins that may have substituents include propylene, 1-hexene, 1-butene, 1-octadecene, allyl alcohol, allylamine, allyl ether, allyl ester, and derivatives thereof. Examples of allyl ethers include diallyl ether and 1,3-diallyloxy-2-propanol. Examples of allyl esters include allyl acetate and diallyl adipate.

[0032] R 3 If is an aromatic hydrocarbon group which may have substituents, examples of monomer (b1) include styrene, 4-methylstyrene, 4-hydroxystyrene, 4-methoxystyrene, and 4-vinylbenzoic acid.

[0033] R of monomer (b1) 3 Examples include an aliphatic hydrocarbon group which may have substituents, -OC(=O)-R4 , -OR 4 and -NH-C(=O)-R 4 At least one selected from the group consisting of is preferred. Here, R 4 R represents an aliphatic hydrocarbon group which may have substituents. 4 Examples include alkyl groups and alkyl groups having substituents. 4 The number of carbon atoms when is an alkyl group is not particularly limited. For example, the number of carbon atoms may be 1 to 24, 4 to 20, or 12 to 18. 4 The structure may be linear or branched. R 4 The substituent in formula (b1) is R 3 The substituents in the "aliphatic hydrocarbon group which may have substituents" can be the same substituents. However, R 4 The substituents in the compound may be electron-withdrawing. Examples of electron-withdrawing groups include ester groups, amide groups, carbamoyl groups, urea groups, thiourea groups, and sulfonamide groups. As monomer (b1), vinyl esters and vinyl ethers are preferred from the viewpoint of having better polymerization properties with monomer (a) and obtaining better liquid repellency, vinyl acetate, vinyl pivalate, vinyl laurate, vinyl stearate, methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, lauryl vinyl ether, and cyclohexyl vinyl ether are more preferred, vinyl acetate, vinyl laurate, vinyl stearate, 4-hydroxybutyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether, and cyclohexyl vinyl ether are even more preferred, and vinyl acetate and vinyl stearate are particularly preferred.

[0034] Monomer (b) may be used alone or in combination of two or more types.

[0035] Polymer (A) may also be a copolymer having units based on the monomer (c) described below (hereinafter also referred to as "unit (c)"). CH2=CX 1 X 2 ···Formula (c) In Formula (c), X 1 , X 2 each independently represent a halogen atom or a hydrogen atom, and X 1 and X 2 are not hydrogen atoms at the same time.

[0036] When the polymer (A) has units (c), the film-forming property of the polymer (A) on a substrate treated with the liquid repellent composition tends to be good. X 1 , X 2 As the halogen atom for X, a chlorine atom is preferable. As the monomer (c), vinyl chloride and vinylidene chloride are preferable. Monomer (c) may be used alone, or two or more kinds may be used in combination.

[0037] The polymer (A) may be a copolymer further having units derived from the following monomer (d). CH2=CR 5 C(=O)OR 6 ···Formula (d)

[0038] In Formula (d), R 5 represents a hydrogen atom or a methyl group, and R 6 represents an optionally substituted monovalent hydrocarbon group. The details and preferred embodiments of the monovalent hydrocarbon group are the same as those described for R 1 and R 2 . R 6 The optional substituent that R may have is not particularly limited as long as it is other than the crosslinkable functional group described later, and examples thereof include aliphatic hydrocarbon groups and aromatic groups.

[0039] As monomer (d), (meth)acrylates having an alkyl group with 1 to 24 carbon atoms are preferred, and (meth)acrylates having an alkyl group with 4 to 22 carbon atoms are more preferred. Examples of (meth)acrylates include alkyl (meth)acrylates such as butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, arachidyl (meth)acrylate, and behenyl (meth)acrylate. As monomer (d), 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate are preferred from the viewpoint of obtaining better liquid repellency. Monomer (d) may be used alone or in combination of two or more types.

[0040] The polymer (A) may be a copolymer further having units based on monomer (e) having a crosslinkable functional group. Monomer (e) is a monomer other than monomer (a), monomer (b), monomer (c), and monomer (d). Preferred crosslinkable functional groups of monomer (e) include functional groups having at least one bond among covalent bonds, ionic bonds, or hydrogen bonds, and functional groups that can form a crosslinked structure through the interaction of said bonds.

[0041] As crosslinkable functional groups, isocyanate groups, blocked isocyanate groups, alkoxysilyl groups, amino groups, alkoxymethylamide groups, methylol groups, silanol groups, ammonium groups, amide groups, epoxy groups, hydroxyl groups, oxazoline groups, carboxyl groups, alkenyl groups, and sulfonic acid groups are preferred due to their excellent wash durability. Among these, epoxy groups, hydroxyl groups, blocked isocyanate groups, alkoxysilyl groups, amino groups, and carboxyl groups are more preferred. Examples of monomer (e) include (meth)acrylates (excluding monomer (d)), acrylamides, vinyl ethers, and vinyl esters.

[0042] As monomer (e), due to its excellent wash durability, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 3,5-dimethylpyrazole adduct of 2-isocyanate-ethyl(meth)acrylate, 2-butanone oxime adduct of 2-isocyanate-ethyl(meth)acrylate, 3,5-dimethylpyrazole adduct of 3-isocyanate-propyl(meth)acrylate, 2-butanone oxime adduct of 3-isocyanate-propyl(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, diacetone acrylamide, glycidyl methacrylate, glycerol(meth)acrylate, polycaprolactone ester of hydroxyethyl(meth)acrylate, phenylglycidyl acrylate and tolylene diisocyanate are used as urethane prepolymers (AT-600, Kyoeisha Co., Ltd.). 2-[1,3,3-trimethyl-5-(1-methylpropylideneaminooxycarbonylamino)-1-cyclohexylmethylaminocarbonyloxy]ethyl methacrylate (Techcoat HE-6P, manufactured by Kyoken Kasei Co., Ltd.) is preferred, N-methylol(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, 3,5-dimethylpyrazole adduct of 2-isocyanateethyl(meth)acrylate, 2-butanone oxime adduct of 2-isocyanateethyl(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, diacetone acrylamide, and glycidyl methacrylate are more preferred, and N-methylol(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, 3,5-dimethylpyrazole adduct of 2-isocyanateethyl(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, and diacetone acrylamide are even more preferred. Monomer (e) may be used alone or in combination of two or more types.

[0043] In terms of making this composition a non-fluorine water repellent, it is preferable that polymer (A) does not contain fluorine atoms. When polymer (A) does not contain fluorine atoms, it can be obtained by polymerizing monomer components that contain monomer (a) which does not contain fluorine atoms and, if necessary, monomers other than monomer (a) which do not contain fluorine atoms.

[0044] The polymer (A) may be a single polymer of monomer (a); or it may be a copolymer of monomer (a) and at least one selected from the group consisting of monomer (b), monomer (c), monomer (d), and monomer (e). A copolymer of monomer (a), monomer (b), monomer (c), monomer (d), and monomer (e) is preferred as the polymer (A).

[0045] However, polymer (A) may further have units based on monomers other than monomer (a), monomer (b), monomer (c), monomer (d), and monomer (e) (hereinafter referred to as "other monomer units"), as long as this does not impair the effects of the invention. Other monomers include norbornene, dicyclopentadiene, and maleic anhydride.

[0046] The proportion of unit (a) is preferably 60% by mass or more, more preferably 70% by mass or more, and may be 100% by mass, relative to the total constituent units of polymer (A). If the proportion of unit (a) is above the lower limit, the liquid repellency is better.

[0047] In the case of polymer (A) being a copolymer having unit (b), the proportion of unit (a) is preferably 5 to 80% by mass, more preferably 8 to 70% by mass, and even more preferably 10 to 60% by mass, relative to the total constituent units of polymer (A). If the proportion of unit (a) is above the lower limit of the above numerical range, the liquid repellency is better. If the proportion of unit (a) is below the upper limit of the above numerical range, it is easier to ensure the reactivity of polymer (A) in the polymerization reaction.

[0048] In the case of polymer (A) being a copolymer having unit (b), the proportion of unit (b) is preferably 20 to 95% by mass, more preferably 25 to 85% by mass, and even more preferably 30 to 80% by mass, relative to the total constituent units of polymer (A). If the proportion of unit (b) is above the lower limit of the above numerical range, the reactivity of polymer (A) in the polymerization reaction is better. If the proportion of unit (b) is below the upper limit of the above numerical range, it is easier to ensure liquid repellency.

[0049] In the case of polymer (A) being a copolymer having unit (c), the proportion of unit (c) is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass, relative to the total constituent units of polymer (A). If the proportion of unit (c) is above the lower limit of the above numerical range, the film-forming properties of polymer (A) are better. If the proportion of unit (c) is below the upper limit of the above numerical range, it is easier to ensure liquid repellency.

[0050] In the case of a copolymer having unit (d), the proportion of unit (d) is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, and even more preferably 1 to 15% by mass, relative to the total constituent units of polymer (A). If the proportion of unit (d) is above the lower limit of the above numerical range, the water repellency is better. If the proportion of unit (d) is below the upper limit of the above numerical range, the stability of the emulsion particles of the polymer formed by emulsion polymerization tends to be good.

[0051] In the case of polymer (A) being a copolymer having unit (e), the proportion of unit (e) is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, and even more preferably 1 to 15% by mass, relative to the total constituent units of polymer (A). If the proportion of unit (e) is above the lower limit of the above numerical range, the washing durability is better. If the proportion of unit (e) is below the upper limit of the above numerical range, the film-forming properties of polymer (A) tend to be good.

[0052] When polymer (A) is a copolymer having other monomer units, the proportion of other monomer units is preferably 0 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 5 to 10% by mass, relative to the total constituent units of polymer (A). If the proportion of other monomer units is above the lower limit of the above numerical range, it is easier to impart properties from the other monomers to polymer (A). If the proportion of other monomer units is below the upper limit of the above numerical range, it is less likely to impair the effects of the invention.

[0053] The proportion of each unit is, 1 The reaction rates of each monomer component can be calculated by 1H-NMR and gas chromatography. When polymer (A) is produced, if the conversion rate of monomer components to polymer (A) is high (e.g., 90% or more), the proportion of each unit may be calculated based on the amount of monomer component charged.

[0054] The Mw of polymer (A) is not particularly limited. For example, it may be 5,000 to 100,000, 7,000 to 80,000, or 10,000 to 100,000. If the Mw of polymer (A) is greater than or equal to the lower limit of the aforementioned numerical range, the liquid-repellent properties are superior. If the Mw of polymer (A) is less than or equal to the upper limit of the aforementioned numerical range, the solubility in liquid solvents is superior.

[0055] The Mn value of polymer (A) is preferably 2,500 to 50,000, more preferably 3,500 to 40,000, and even more preferably 5,000 to 25,000. If the Mn value of polymer (A) is above the lower limit of the above numerical range, the liquid repellency is better. If the Mn value of polymer (A) is below the upper limit of the above numerical range, the film-forming properties of polymer (A) are better.

[0056] (Liquid medium) From the viewpoint of applicability, it is preferable that this composition further contains a liquid medium. Examples of liquid media include water, organic solvents, and aqueous media.

[0057] Examples of organic solvents include water-soluble organic solvents, ketones, compounds having amide bonds, compounds having ether bonds but lacking hydroxyl groups, and aromatic hydrocarbon compounds. Water-soluble organic solvents will be discussed later. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of compounds having an amide bond include dimethylacetamide, 3-methoxydimethylpropanamide, 3-butoxydimethylpropanamide, and methylpyrrolidone. Examples of compounds having an ether bond and lacking a hydroxyl group include tetrahydrofuran, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and cyclopentyl methyl ether. Examples of aromatic hydrocarbon compounds include toluene and xylene. Organic solvents may be used individually or in combination of two or more types.

[0058] Among these, organic solvents capable of dissolving or dispersing polymer (A) are preferred, and those capable of dissolving polymer (A) are more preferred. From the viewpoint of good compatibility with polymer (A), organic solvents are preferably ketones; compounds having an ether linkage and not having a hydroxyl group; and acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, and cyclopentyl methyl ether are more preferred.

[0059] Examples of aqueous media include water-soluble organic solvents and mixtures of water and water-soluble organic solvents. A water-soluble organic solvent is an organic solvent that is miscible with water in any proportion. The water-soluble organic solvent may be any compound that is miscible with water in any proportion, and may be selected from the group consisting of ketones, compounds having amide bonds, compounds having ether bonds but lacking hydroxyl groups, and aromatic hydrocarbon compounds. 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 1-methoxy-2-propanol, 3-methoxymethylbutanol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol. Examples of aprotic polar solvents include N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, acetone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-3-methyl-1-butanol, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. Aqueous media may be used individually or in combination of two or more types.

[0060] When the aqueous medium is a mixture of water and a water-soluble organic solvent, the content of the water-soluble organic solvent is preferably 1 to 80 parts by mass, and more preferably 5 to 60 parts by mass, per 100 parts by mass of water.

[0061] (Low molecular component) This composition may further contain low molecular weight components with an Mw of less than 5000. In one embodiment, when the polymerizability of monomer (a) is difficult to obtain, low molecular weight components with an Mw of less than 5000 may contribute to the development of liquid repellency. In this case, components with an Mw of 5000 or more are referred to as high molecular weight components.

[0062] Examples of low molecular weight components include the monomers (a), (b), (c), (d), (e) mentioned above, and polymer (A) with an Mw of less than 5000. Details and preferred embodiments of each monomer are as described above. Each monomer and polymer (A) as a low molecular weight component may be used individually or in combination of two or more. If the composition contains monomer (a) as a low molecular weight component, monomer (a) in the composition and monomer (a) that forms unit (a) of polymer (A) may be the same or different.

[0063] The Mw of polymer (A) as a low molecular weight component is preferably 1,000 or more and less than 5,000, more preferably 1,200 to 4,800, and even more preferably 1,500 to 3,000. The Mn of polymer (A) as a low molecular weight component is preferably 500 to 2,500, and more preferably 750 to 1,500.

[0064] The polymer (A) as a low molecular weight component may further have at least one selected from the group consisting of units (b), (c), (d), and (e), as needed. The proportion of each unit in polymer (A) as a low molecular weight component, the details of the copolymer composition, and preferred embodiments are the same as those described for polymer (A).

[0065] (Other ingredients) This composition may further contain other components besides polymer (A), low molecular weight components, and liquid media, as needed. Other components include, for example, surfactants, polymers other than polymer (A), non-fluorinated water and oil repellents, water-soluble polymer resins, crosslinking agents, catalysts, penetrating agents, defoaming agents, film-forming aids, insecticides, flame retardants, antistatic agents, wrinkle inhibitors, softeners, pH adjusters, paper strength agents, water-resistant agents, adhesives, organic fillers, inorganic fillers, support agents, flocculants, buffering agents, disinfectants, biocides, and metal ion chelating agents. In addition, various additives described in Japanese Patent Publication No. 2006-328624, Japanese Patent Publication No. 2015-172198, and Japanese Patent Publication No. 2017-025440, etc., can be listed without limitation as other components. Other ingredients may be used individually or in combination of two or more.

[0066] As the surfactant, a surfactant that does not contain a fluorine atom is preferred. Examples of surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Each of these surfactants may be used individually or in combination of two or more.

[0067] As for the surfactant, due to its excellent dispersion stability of the aqueous dispersion containing polymer (A), the use of a nonionic surfactant alone, a combination of a nonionic surfactant and a cationic surfactant, a combination of a nonionic surfactant and an amphoteric surfactant, and the use of an anionic surfactant alone are preferred, with the combination of a nonionic surfactant and a cationic surfactant being more preferred.

[0068] The ratio of nonionic surfactant to cationic surfactant (nonionic surfactant / cationic surfactant) is preferably 100 / 0 to 40 / 60 (mass ratio), and more preferably 97 / 3 to 40 / 60 (mass ratio). In certain combinations of nonionic and cationic surfactants, the total amount of surfactants per 100 parts by mass of polymer (A) may be 5 parts by mass or less. In this case, the adverse effect of surfactants on the liquid repellency of articles treated with this composition is easily reduced.

[0069] Examples of nonionic surfactants include the surfactants described in paragraphs

[0067] to

[0095] of Japanese Patent Publication No. 2009-215370. 1 ~s 6 These are some examples. Surfactants 1 Polyoxyethylene alkyl ethers are preferred as such. Surfactants 2 As such, acetylene glycol ethylene oxide adducts are preferred. Surfactants 3 As such, ethylene oxide propylene oxide polymers are preferred.

[0070] Examples of cationic surfactants include the surfactants described in paragraphs

[0096] to

[0100] of Japanese Patent Publication No. 2009-215370. 7 These are some examples. Surfactants 7 Preferably, the compound is 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, and compound (4) is more preferred. [(R 7 )4N + ]·Z - Formula (4)

[0071] However, R 7 These are polyoxyalkylene chains consisting of a hydrogen atom, an alkyl group with 1 to 22 carbon atoms, an alkenyl group with 2 to 22 carbon atoms, or a hydroxyl group at the end. 7 These may be the same or different, but the four R's 7 It is not a hydrogen atom at the same time.

[0072] Z - Z is the counterion. - Examples include chloride ions, ethyl sulfate ions, and acetate ions. Examples of compound (4) include monostearyltrimethylammonium chloride, monostearyldimethylmonoethylammonium ethyl sulfate, mono(stearyl)monomethyldi(polyethylene glycol)ammonium chloride, di(tallow alkyl)dimethylammonium chloride, and dimethylmonococonutamine acetate.

[0073] Examples of amphoteric surfactants include the surfactants described in paragraphs

[0101] to

[0102] of Japanese Patent Publication No. 2009-215370. 8 These are some examples.

[0074] As for the combination of surfactants, surfactants s are chosen because they have little adverse effect on the liquid repellency of the articles treated with this composition, and the dispersion stability of the dispersion containing polymer (A) is excellent. 1 and surfactants 2 and surfactants 7 In combination with surfactants 1 and surfactants 3 and surfactants 7 In combination with surfactants 1 and surfactants 2 and surfactants 3 and surfactants 7 A combination with the following is preferred. In these combinations, surfactants s 7 It is more preferable that it is compound (4).

[0075] Examples of polymers other than polymer (A) include polymers having at least one selected from the group consisting of units (b), (c), (d), (e), and other monomer units, and not having unit (a) (hereinafter also referred to as "polymer (B)").

[0076] The Mw of polymer (B) may be between 5,000 and 100,000, or between 10,000 and 80,000. The Mn of polymer (B) may be between 2,500 and 50,000, or between 5,000 and 40,000.

[0077] Examples of water-soluble polymer resins include hydrophilic polyesters and their derivatives, and hydrophilic polyethylene glycols and their derivatives. A single water-soluble polymer resin may be used, or two or more may be used in combination.

[0078] Examples of crosslinking agents include those described in paragraphs

[0060] to

[0063] of International Publication No. 2019 / 172021. Examples of catalysts include the crosslinking agents described in paragraph

[0064] of International Publication No. 2019 / 172021. The crosslinking agent and catalyst may be used individually or in combination of two or more types.

[0079] (Content of each component) If the composition contains a liquid medium, the amount of the liquid medium can be appropriately selected according to the desired solid content concentration of the composition. The solid content concentration of this composition is preferably 0.1 to 7% by mass, and more preferably 0.2 to 5% by mass, when this composition is used for processing articles.

[0080] The content of polymer (A) in this composition is preferably 60% by mass or more, more preferably 70% by mass or more, and may be 100% by mass, based on 100% by mass of the solid content of this composition. If the content of polymer (A) is within the above numerical range, liquid repellency is easily obtained when an article is treated with this composition.

[0081] The total content of low molecular weight components in this composition is preferably 0 to 30% by mass, more preferably 0.1 to 25% by mass, even more preferably 0.5 to 20% by mass, and particularly preferably 1.0 to 15% by mass, relative to the total mass of high molecular weight and low molecular weight components. If the content of low molecular weight components is within the above numerical range, oil repellency is easily obtained when an article is treated with this composition. The content of monomer (a) as a low molecular weight component is preferably 0 to 30% by mass, more preferably 0.1 to 25% by mass, even more preferably 0.5 to 20% by mass, and particularly preferably 1.0 to 15% by mass, relative to the total mass of the high molecular weight component and the low molecular weight component. If the content of monomer (a) is within the above numerical range, oil repellency is easily obtained when an article is treated with this composition. The content of polymer (A) as a low molecular weight component is preferably 0 to 30% by mass, more preferably 0.1 to 25% by mass, even more preferably 0.5 to 20% by mass, and particularly preferably 1.0 to 15% by mass, relative to the total mass of the high molecular weight component and the low molecular weight component. If the content of polymer (A) as a low molecular weight component is within the above numerical range, oil repellency is easily obtained when an article is treated with this composition.

[0082] The total content of high-molecular-weight and low-molecular-weight components is preferably 60% by mass or more, more preferably 70% by mass or more, and may also be 100% by mass, based on 100% by mass of the solid content of the composition.

[0083] The content of polymer (A) is preferably 0.01 to 50% by mass, more preferably 0.05 to 40% by mass, and even more preferably 0.1 to 35% by mass, based on 100% by mass of the composition. If the content of polymer (A) is above the lower limit of the above numerical range, the composition is likely to impart liquid repellency to articles. If the content of polymer (A) is below the upper limit of the above numerical range, the stability over time of the polymer (A) solution and the polymer (A) emulsion particles tends to be good.

[0084] (Method for producing a liquid-repellent composition) This composition can be produced, for example, by polymerizing a monomer component containing at least monomer (a) in the presence of a polymerization initiator. The monomeric component may further include at least one selected from the group consisting of monomer (b), monomer (c), monomer (d), monomer (e), and other monomers.

[0085] Details and preferred embodiments of each monomer are as described above. Furthermore, the details and preferred embodiments of the proportion of each monomer in the monomer components are the same as those described for the proportion of each unit of polymer (A).

[0086] Examples of polymerization initiators include thermal polymerization initiators, photopolymerization initiators, radiation polymerization initiators, radical polymerization initiators, and ionic polymerization initiators. Among these, radical polymerization initiators are preferred. Examples of radical polymerization initiators include azo polymerization initiators, peroxide polymerization initiators, and redox initiators, which are used depending on the polymerization temperature. Azo compounds are preferred as radical polymerization initiators, and salts of azo compounds are more preferred. The polymerization temperature is preferably 20 to 150°C. The amount of polymerization initiator used 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 monomer component.

[0087] When polymerizing monomer components, molecular weight modifiers may be used. Examples of molecular weight modifiers include aromatic compounds, mercapto alcohols, mercaptocarboxylic acids, and alkyl mercaptans. Among these, mercaptocarboxylic acids and alkyl mercaptans are preferred. Examples of molecular weight modifiers include mercaptoethanol, mercaptopropionic acid, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, stearyl mercaptan, and α-methylstyrene dima (CH2=C(Ph)CH2C(CH3)2Ph). The amount of molecular weight adjusting agent used is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and may even be 0 parts by mass, per 100 parts by mass of monomer component.

[0088] Examples of polymerization methods for monomer components include emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization. Among these, emulsion polymerization, solution polymerization, and bulk polymerization are preferred. Emulsion polymerization can be carried out, for example, by the methods described in Japanese Patent Publication No. 8-3113, Japanese Patent Publication No. 2006-328624, Japanese Patent Publication No. 2015-172198, and Japanese Patent Publication No. 2017-025440, respectively. Solution polymerization can be carried out, for example, by the method described in International Publication No. 2020 / 045407. After polymerization, other components or liquid media may be added as needed.

[0089] (Mechanism of action) As described above, this composition contains polymer (A) having unit (a), and therefore exhibits excellent liquid-repellent properties despite being hydrocarbon-based. Conventionally, non-fluorinated polymers having long-chain alkyl (meth)acrylate units, which have been proposed as hydrocarbon-based water repellents, have methylene groups present in the main chain when the long-chain alkyl (meth)acrylate units polymerize. Therefore, it is thought that sufficient liquid repellency was not achieved because the distance between the long-chain alkyl groups in the side chains was too large. In this composition, when monomer (a) is polymerized, there are no methylene groups in the main chain. Therefore, the monovalent hydrocarbon groups with 8 to 24 carbon atoms, which are the side chains of unit (a), are located at a closer distance than when conventional long-chain alkyl (meth)acrylate units are polymerized, resulting in excellent liquid repellency.

[0090] [Method for processing the substrate] In the method for treating a substrate according to the present invention, the substrate is treated with this composition. Examples of substrates include fibers, fabrics, textile products, glass, silicon wafers, paper substrates, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded products, and porous articles. Examples of woven fabrics include woven fabrics, knitted fabrics, nonwoven fabrics, and napped fabrics. Textile products include, for example, clothing such as ski wear, rainwear, coats, blousons, windbreakers, down jackets, sportswear, work clothes, uniforms, and protective clothing, as well as backpacks, bags, and tents. Examples of paper include paper, cardboard, pulp molds, synthetic paper using synthetic fibers as at least part of the raw materials, and related products. Porous articles are used, for example, as filters. Examples of materials for porous articles include polypropylene, polyethylene terephthalate, polytetrafluoroethylene, glass fibers, cellulose nanofibers, carbon fibers, and cellulose acetate.

[0091] When the base material is a fiber, fabric, or textile product comprising a fabric, the type of fiber is not particularly limited. Examples include natural fibers such as cotton, wool, silk, or cellulose; synthetic fibers such as polyester, polyamide, acrylic, or aramid; regenerated fibers such as rayon, viscose rayon, or lyocell; blended fibers of natural and synthetic fibers; and blended fibers of natural and regenerated fibers. Examples of materials when the base material is a nonwoven fabric include polyethylene, polypropylene, polyolefin, polyethylene terephthalate, polytetrafluoroethylene, glass, and rayon. The thickness of the textile fabric is not particularly limited. For example, it can be 0.01 to 5 mm.

[0092] Any method that allows the composition to adhere to the substrate is acceptable. If the composition contains a liquid medium, examples of methods that apply the composition to the substrate include coating, impregnation, immersion, spraying, brush padding, sizing press, and roller application, followed by drying. The amount of solid content in this composition to be attached to the substrate is not particularly limited. For example, in the case of textile fabrics, 0.001 to 0.05 g per gram of textile fabric is preferred. Drying may be carried out at room temperature or by heating, with heating being preferred. When heating, the heating temperature is not particularly limited, but for example, it is 80 to 200°C.

[0093] [Goods] The articles of the present invention have a substrate treated with this composition. Therefore, the articles of the present invention have a coating film with excellent liquid-repellent properties. Details and preferred embodiments of the substrate are the same as those described in the section on the substrate treatment method. The articles of the present invention can be manufactured, for example, by the substrate treatment method described above. [Examples]

[0094] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. "Part" refers to "parts by mass". Examples 1-3 and 7-11 are examples of actual cases. Examples 4-6 and 12 are comparative examples.

[0095] [Abbreviation] Monomer (a): DSTF: Distearyl fumarate Monomer (b): VSt: Vinyl stearate Monomer (c): VdCl: Vinylidene chloride Monomer (d): STA: Stearyl acrylate Monomer (e): MOI-BP: 3,5-dimethylpyrazole adduct of 2-isocyanate ethyl methacrylate (see compound (5) below)

[0096] [ka]

[0097] Poly-DSTF: Polydistearyl fumarate (Mw: 14,000, Mn: 10,000) PMMA: Polymethyl methacrylate (Mw: 40,000, Mn: 28,000) Poly-STA: Polystearyl acrylate (Mw: 19,000, Mn: 11,000)

[0098] Polymerization initiator: VA-061A: 10% by mass aqueous solution of acetate of 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (manufactured by Wako Pure Chemical Industries, Ltd., VA-061) Molecular weight modifier: nStSH:n-octadecyl mercaptan Surfactants 1 : E-420: Polyoxyethylene (13) oleyl ether (manufactured by Kao Corporation, Emulgen 420) Surfactants 3 : P-204: Ethylene oxide propylene oxide polymer (manufactured by Nippon Oil & Fats Co., Ltd., Pronon 204) Surfactants 7 : AQ-18: Stearyltrimethylammonium chloride (manufactured by Lion Corporation, Lipocard 18-63, active ingredient: 63% by mass isopropyl alcohol solution) Liquid medium: DPG: Dipropylene glycol Crosslinking agent: Mekkanate TP-10: Blocked Isocyanate (manufactured by Meisei Chemical Industry Co., Ltd.)

[0099] [Measurement methods, evaluation methods] (Mw, Mn of polymer (A)) A solution of tetrahydrofuran containing the polymer at a concentration of 1.0% by mass was passed through a 0.2 μm pore size filter to obtain an analytical sample. Mw and Mn were measured for this analytical sample. The molecular weight distribution was determined as the value of Mw relative to Mn (Mw / Mn). The measurement conditions were as follows. • Equipment: Tosoh Corporation, HLC-8220GPC • Columns: TSKgel SuperHZ-4000, TSKgel SuperHZ-3000, TSKgel SuperHZ-2500, and TSKgel SuperHZ-2000 were used in series. ·Measurement temperature: 40℃ ·Injection volume: 40μL ·Outflow rate: 0.35mL / min • Eluent: Tetrahydrofuran • Standard sample: PStQuick Kit-M (standard polystyrene sample with known molecular weight), manufactured by Tosoh Corporation.

[0100] (Test fabric for evaluating water repellency and wash durability) Dyed nylon fabric, PET fabric, and cotton were each immersed in the respective liquid-repellent compositions and squeezed until a wet pickup of 60% by mass was achieved. Subsequently, they were dried at 110°C for 90 seconds, followed by drying at 170°C for 60 seconds to obtain the test fabrics.

[0101] (water repellency) The water repellency of the test fabric was evaluated according to the spray test of JIS L1092-2009. Water repellency was expressed on a 5-point scale from 1 to 5. A higher score indicates better water repellency. A "+" next to a grade indicates that the properties are slightly better than the standard for that grade. A "-" next to a grade indicates that the properties are slightly worse than the standard for that grade.

[0102] (Washing durability) The test fabrics were washed 20 or 50 times according to the washing method specified in JIS L0217 Appendix 103. After washing, the test fabrics were air-dried overnight in a room at 25°C and 60% humidity. The water repellency of the test fabrics was then evaluated as described above, and the wash durability was assessed accordingly.

[0103] [Synthesis Example 1: DSTF Synthesis] A first mixture was obtained by adding 56.8 g (210 mmol) of stearyl alcohol, 30.4 g (300 mmol) of triethylamine, and 400 mL of chloroform to a 1 L three-necked flask. Subsequently, a second mixture of 15.3 g (100 mmol) of fumaryl chloride and 100 mL of chloroform was added dropwise to the first mixture at 0°C under a nitrogen atmosphere. The mixture was then stirred at room temperature for 1 hour to obtain the reaction mixture. The obtained reaction mixture was transferred to a 1 L separatory funnel, and the organic layer was washed with 1 N hydrochloric acid aqueous solution, followed by washing with saturated brine. The obtained organic layer was dried over sodium sulfate and concentrated, and then purified by silica gel column chromatography using chloroform:hexane = 5:5 (volume ratio) as the developing solvent to obtain DSTF. The yield was 14.6g, and the yield was 25%. 1 The H-NMR spectrum is shown below. 1 H-NMR (solvent: CDCl3, 400MHz): δ6.85ppm (2H, s), δ4.19ppm (4H, t, J=6.8Hz), δ1.71-1.64ppm (4H, m), δ1.39-1.22ppm (60H, m), δ0.88ppm (6H, t, J=6.8Hz)

[0104] [ka]

[0105] [Synthesis Example 2: Synthesis of Poly-DSTF] 1 g of DSTF and 0.01 g of dimethyl-2,2'-azobis(2-methylpropionate) (Wako Pure Chemical Industries, Ltd.) were placed in a 30 mL ampoule and shaken at 80°C for 24 hours. The resulting crude solution was added dropwise to methanol, and the precipitate was filtered off to obtain white solid Poly-DSTF.

[0106] [Examples 1-6] According to the formulations shown in Table 1, high molecular weight and low molecular weight components were dissolved in cyclopentyl methyl ether to obtain an oil-repellent composition with a solid content of 1% by mass. A silicon wafer measuring 3 cm x 3 cm, which had been cleaned with isopropyl alcohol, was coated with an oil-repellent composition by spin coating and dried at 40°C for 1 hour to form a coating film.

[0107] The static contact angle with n-hexadecane (hereinafter also referred to as "hexadecane contact angle") was measured at three points on the surface of the formed coating film: the center, left edge, and right edge. The average value of the three points was then calculated. The hexadecane contact angle was measured at 20°C in accordance with JIS R 3257:1999, by placing 2 μL of n-hexadecane droplets at each of the three points on the surface of the coating film (center, left edge, and right edge) and measuring each droplet using the drop method. The results are shown in Table 1.

[0108] [Table 1]

[0109] The coating films of the oil-repellent compositions in Examples 1-3 had a larger hexadecane contact angle and superior oil repellency compared to Examples 4-6.

[0110] [Example 7] In a polypropylene cup, 14.0g of DSTF, 16.5g of VSt, 1.1g of MOI-BP, 0.3g of StSH, 0.9g of E-420, 0.2g of P-204, 0.3g of AQ-18, 10.3g of DPG, and 57.7g of deionized water were placed and heated at 80°C for 10 minutes. After that, the mixture was obtained by mixing using a homomixer (Biomixer, manufactured by Nippon Seiki Seisakusho Co., Ltd.). The resulting mixture was processed at 40 MPa using a high-pressure emulsifier (APV Lannier, Minilab) to obtain an emulsion. 100 g of the obtained emulsion was placed in a glass ampoule and cooled to below 40°C. 0.9 g of VA-061A was added, and 2.6 g of VdCl was introduced. Polymerization was carried out at 60°C for 15 hours with stirring to obtain a copolymer emulsion. Approximately 10 g of acetone was added dropwise to 1 g of the obtained emulsion, and the mixture was heated and stirred at 50°C, then cooled to precipitate a solid. The obtained solid was recovered by vacuum filtration to obtain the copolymer. The Mw and Mn of the copolymer obtained in this way were measured. The resulting copolymer emulsions were diluted with distilled water to adjust the solid content concentrations to 0.5% by mass, 1.0% by mass, and 1.5% by mass, respectively. Then, Mekkanate TP-10 was added to each emulsion concentration to a total concentration of 1.5% by mass to prepare liquid-repellent compositions. The water repellency (water repellency after air drying) and water repellency after washing were evaluated for the liquid-repellent compositions.

[0111] [Examples 8-12] Copolymer emulsions were obtained in the same manner as in Example 7, except that the amounts of each raw material were changed to the amounts shown in Table 2. Mw and Mn were measured from each emulsion in the same manner as in Example 7. In Example 8, STA was placed in a polypropylene cup as the monomer component at the start of the reaction. For each copolymer emulsion obtained in the example, a liquid-repellent composition was prepared in the same manner as in Example 7, and the water repellency (water repellency after air drying) and water repellency after washing were evaluated.

[0112] [Table 2]

[0113] [Table 3]

[0114] Table 2 shows the measurement results of Mw, Mn, and Mw / Mn for each copolymer, along with the proportion of each monomer in the monomer components. Table 3 shows the evaluation results of water repellency and wash durability for each example. Examples 7 to 11 achieved water repellency and wash durability equivalent to or better than that of Example 12. [Industrial applicability]

[0115] The present invention provides a hydrophobic composition that can impart excellent hydrophobicity despite being hydrocarbon-based; a method for treating a substrate using the hydrophobic composition; and an article having a coating film that exhibits excellent hydrophobicity despite being hydrocarbon-based.

[0116] This application claims priority based on Japanese Patent Application No. 2021-069286, filed on April 15, 2021, and the entire contents of the said Japanese application are incorporated herein by reference.

Claims

1. A liquid repellent composition comprising a polymer (A) having units based on monomer (a) represented by the following formula (a), wherein the polymer (A) does not contain fluorine atoms. (R １ -Q １ -)HC=CH(-Q ２ -R ２ ) Formula (a) In formula (a), Q １ and Q ２ Each of these independently represents a divalent linking group, R １ and R ２ Each of these independently represents a monovalent hydrocarbon group having 8 to 24 carbon atoms.

2. The Q of the monomer (a) １ and Q ２ are each independently -C(=O)-, -C(=O)-O-, -O-C(=O)-, or -C(=O)-NH-, the liquid repellent composition according to claim 1.

3. R of monomer (a) １ and R ２ The liquid-repellent composition according to claim 1, wherein each is independently a monovalent hydrocarbon group having 12 to 24 carbon atoms.

4. The liquid-repellent composition according to claim 1, wherein the polymer (A) is a copolymer further having units based on the monomer (b) described below. Monomer (b): A monomer other than monomer (a), which has one polymerizable unsaturated group and an electron-donating group adjacent to the polymerizable unsaturated group in one molecule.

5. The liquid repellent composition according to claim 4, wherein the monomer (b) is the monomer (b1) represented by the following formula (b1). CH ２ =CHR ３ ・・・Form (b1) In formula (b1), R ３ It is an electron-donating group.

6. The electron-donating group may have substituents, such as an aliphatic hydrocarbon group, -O-C(=O)-R ４ , -O-R ４ , and -NH-C(=O)-R ４ The liquid repellent composition according to claim 5, wherein it is at least one selected from the group consisting of the following. Here, R ４ This represents an aliphatic hydrocarbon group which may have substituents.

7. The liquid repellent composition according to claim 4, wherein the proportion of units based on the monomer (a) is 5 to 80% by mass with respect to the total constituent units of the polymer (A).

8. The liquid repellent composition according to claim 4, wherein the proportion of units based on monomer (b) is 20 to 95% by mass with respect to all constituent units of polymer (A).

9. The proportion of units based on the monomer (a) is 5 to 80% by mass relative to the total constituent units of the polymer (A). The liquid repellent composition according to claim 4, wherein the proportion of units based on monomer (b) is 20 to 95% by mass with respect to all constituent units of polymer (A).

10. The liquid-repellent composition according to claim 1, wherein the polymer (A) is a copolymer further having units based on monomer (c) represented by the following formula (c). CH ２ =CX １ X ２ ・・・Form (c) In formula (c), X １ , X ２ Each of these independently represents either a halogen atom or a hydrogen atom, X １ and X ２ It is not a hydrogen atom at the same time.

11. The liquid repellent composition according to claim 10, wherein the monomer (c) is at least one selected from the group consisting of vinyl chloride and vinylidene chloride.

12. The liquid-repellent composition according to claim 1, wherein the polymer (A) is a copolymer further having units based on monomer (d) represented by the following formula (d). CH ２ =CR ５ C(=O)OR ６ ... Formula (d) In formula (d), R ５ R represents a hydrogen atom or a methyl group. ６ This represents a monovalent hydrocarbon group which may have substituents.

13. The liquid repellent composition according to claim 1, wherein the polymer (A) is a copolymer further having units based on a monomer (e) having a crosslinkable functional group.

14. A method for treating a substrate, comprising treating the substrate with a liquid-repellent composition according to any one of claims 1 to 13.

15. An article having a substrate treated with a liquid-repellent composition according to any one of claims 1 to 13.

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