Water repellent composition, method for producing non-fluoropolymer, treatment method, and article

Abstract

The present invention relates to a water repellent composition comprising a non-fluoropolymer, the non-fluoropolymer has a structural unit based on a long-chain alkyl (meth) acrylate monomer, a structural unit based on a halogenated ethylene monomer, a structural unit based on a (meth) acrylate monomer having a blocked isocyanate structure, and a structural unit based on a (meth) acrylamide monomer having a specific structure. The proportion of the unit based on the (meth) acrylate monomer having a blocked isocyanate structure is 0.5-10% by mass and the proportion of the structural unit based on the (meth) acrylamide monomer is 0.5-10% by mass with respect to the total amount of the structural units of the non-fluoropolymer.

Description

Technical Field

[0001] The present invention relates to a water repellent composition, a method for producing a non-fluoropolymer, a treatment method, and an article.

[0002] This application claims priority based on Japanese Patent Application No. 2022-186730 filed in Japan on November 22, 2022, and incorporates its content herein. Background Art

[0003] As a method for imparting water repellency to the surface of articles such as fiber products, a method of treating an article with a water repellent composition containing a fluoropolymer is known. However, there are concerns about the high environmental burden of the fluoropolymer used in the above method. Therefore, there is a demand for a water repellent composition containing a non-fluoropolymer that can impart sufficient water repellency to the surface of an article and has a low environmental burden.

[0004] As a water repellent composition containing a non-fluoropolymer, for example, Patent Document 1 discloses a water repellent composition containing a non-fluorocopolymer, which is characterized in that it does not have a polyfluoroalkyl group, but has a structural unit based on a (meth)acrylate monomer (A) having an alkyl group with 20 to 30 carbon atoms and a structural unit based on a haloolefin monomer (B). The proportion of the structural unit based on monomer (A) is 5 to 95% by mass in all structural units (100% by mass), the proportion of the structural unit based on monomer (B) is 5 to 60% by mass in all structural units (100% by mass), and the total of the content ratios of the structural unit based on monomer (A) and the structural unit based on monomer (B) is 65% by mass or more of all structural units (100% by mass).

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: WO 2009 / 113589 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] If an article treated with a water repellent treatment is used for a long time, the water repellency sometimes decreases due to abrasion of the water repellent film formed on the surface of the article. Therefore, there is a demand for a water repellent composition containing a non-fluorocopolymer that can obtain a water repellent film with excellent durability against abrasion (hereinafter, also referred to as "abrasion durability"), that is, a water repellency that is not easily reduced by abrasion. The abrasion durability of the water repellent composition described in Patent Document 1 is insufficient.

[0010] An object of the present invention is to provide a water repellent composition capable of obtaining an article with more excellent abrasion durability, a method for producing a non-fluoropolymer, a treatment method using the above water repellent composition, and an article with excellent abrasion durability treated with the above water repellent composition.

[0011] Means for solving the problems

[0012] The present invention has the following aspects.

[0013] [1] A water repellent composition comprising a non-fluoropolymer having a structural unit based on a (meth)acrylic long-chain alkyl ester monomer, a structural unit based on a vinyl halide monomer, a structural unit based on a (meth)acrylate monomer having a blocked isocyanate structure, and a structural unit based on a (meth)acrylamide monomer represented by the following formula (1). The proportion of the structural unit based on the (meth)acrylic long-chain alkyl ester monomer is 70 to 94% by mass, 72 to 92% by mass, or 74 to 90% by mass, the proportion of the structural unit based on the vinyl halide monomer is 5 to 20% by mass, 6 to 15% by mass, or 6 to 12% by mass, the proportion of the unit based on the (meth)acrylate monomer having a blocked isocyanate structure is 0.5 to 10% by mass, 0.6 to 8% by mass, or 0.8 to 6% by mass, and the proportion of the structural unit based on the (meth)acrylamide monomer is 0.5 to 10% by mass, 0.6 to 8% by mass, or 0.8 to 6% by mass, relative to the total amount of the structural units of the non-fluoropolymer.

[0014] (R 3 )2-N-R 2 -C(=O)CR 1 =CH2 (1)

[0015] In the above formula (1), R 1 represents H, CH3 or a chlorine atom, preferably H or CH3, more preferably H, R 2 represents a single bond or a divalent organic group having 1 to 6 carbon atoms, preferably a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms, more preferably a single bond or a divalent alkylene group having 1 to 3 carbon atoms, and further preferably a single bond, R 3 represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 or 2 carbon atoms, and multiple Rs 3 may be the same or different.

[0016] [2] The water repellent composition according to [1], wherein the (meth)acrylic long-chain alkyl ester monomer is represented by the following formula (2).

[0017] R 5 -OC(=O)CR 4 =CH2 (2)

[0018] In the aforementioned formula (2), R 4 represents H, CH3, or a chlorine atom, preferably H or CH3, more preferably H, and R 5 represents an alkyl group having 12 to 30 carbon atoms, 14 to 28 carbon atoms, or 16 to 24 carbon atoms.

[0019] [3] The water repellent composition according to [2], wherein the structural unit based on the (meth)acrylic acid long-chain alkyl ester monomer contains the structural unit of the (meth)acrylic acid long-chain alkyl ester monomer having 12 to 18 carbon atoms, 16 to 18 carbon atoms, or 18 carbon atoms based on R 5 in the aforementioned formula (2) and the structural unit of the (meth)acrylic acid long-chain alkyl ester monomer having 19 to 30 carbon atoms, 20 to 28 carbon atoms, or 20 to 24 carbon atoms based on R 5 in the aforementioned formula (2).

[0020] [4] The water repellent composition according to [3], wherein, relative to the total amount of the structural unit based on the (meth)acrylic acid long-chain alkyl ester monomer, the proportion of the structural unit of the (meth)acrylic acid long-chain alkyl ester monomer having 19 to 30 carbon atoms, 20 to 28 carbon atoms, or 20 to 24 carbon atoms based on R 5 in the aforementioned formula (2) is 50 to 99% by mass, 55 to 99% by mass, 60 to 95% by mass, or 62 to 90% by mass.

[0021] [5] The water repellent composition according to any one of [1] to [4], wherein the aforementioned vinyl halide monomer is vinyl chloride or vinylidene chloride.

[0022] [6] The water repellent composition according to any one of [1] to [5], wherein the aforementioned (meth)acrylate monomer having a blocked isocyanate structure is 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate or 2-[0-(1'-methylpropylideneamino)carboxylamino]ethyl methacrylate.

[0023] [7] The water repellent composition according to any one of [1] to [6], wherein the aforementioned (meth)acrylamide monomer is at least one monomer selected from the group consisting of N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dimethylaminoethylacrylamide, N,N-dimethylaminopropylacrylamide, N,N-diethylaminoethylacrylamide, and N,N-diethylaminopropylacrylamide.

[0024] [8]A method for producing a non-fluorinated polymer, which polymerizes a mixture containing a long-chain alkyl (meth)acrylate monomer, a vinyl halide monomer, a (meth)acrylate monomer having a blocked isocyanate structure, and a (meth)acrylamide monomer represented by the following formula (3) in the presence of a surfactant and a polymerization initiator, wherein, based on the total mass of all the monomers constituting the non-fluorinated polymer, the proportion of the long-chain alkyl (meth)acrylate monomer is 70 to 94% by mass, 72 to 92% by mass, or 74 to 90% by mass, the proportion of the vinyl halide monomer is 5 to 20% by mass, 6 to 15% by mass, or 6 to 12% by mass, the proportion of the (meth)acrylate monomer having a blocked isocyanate structure is 0.5 to 10% by mass, 0.6 to 8% by mass, or 0.8 to 6% by mass, and the proportion of the (meth)acrylamide monomer is 0.5 to 10% by mass, 0.6 to 8% by mass, or 0.8 to 6% by mass.

[0025] (R 3’ )2-N-R 2’ -C(=O)CR 1’ =CH2 (3)

[0026] In the above formula (3), R 1’ represents H, CH3 or a chlorine atom, preferably H or CH3, more preferably H, R 2’ represents a single bond or a divalent organic group having 1 to 6 carbon atoms, preferably a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms, more preferably a single bond or a divalent alkylene group having 1 to 3 carbon atoms, and further preferably a single bond, R 3’ represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 or 2 carbon atoms, and multiple Rs 3’ may be the same or different optionally.

[0027] [9]A treatment method using the water repellent composition according to any one of [1] to [7].

[0028]

[10] An article treated with the water repellent composition according to any one of [1] to [7].

[0029] Effects of the Invention

[0030] According to the present invention, it is possible to provide a water repellent composition, a method for producing a non-fluorinated polymer, a treatment method using the foregoing water repellent composition, and an article having excellent abrasion durability treated with the foregoing water repellent composition, from which an article with more excellent abrasion durability can be obtained. Detailed Embodiments

[0031] The meanings and definitions of the terms in this specification are as follows.

[0032] "Non-fluorine polymer" is a general term for polymers in which the content of fluorine atoms is 0.1% by mass or less relative to the total mass of the polymer. The content of fluorine atoms relative to the total mass of the polymer can be measured by combustion ion chromatography or the like.

[0033] "Structural unit based on a monomer" is a general term for atomic groups directly formed by polymerization of one molecule of a monomer and atomic groups obtained by chemical conversion of a part of the aforementioned atomic groups.

[0034] "(Meth)acrylate" is a general term for acrylate, methacrylate, and compounds in which the methyl group in the methacryloyl group of the aforementioned methacrylate is replaced by a chlorine atom. Similarly, "(meth)acryloyl group" is a general term for an acryloyl group, a methacryloyl group, and a group obtained by replacing the methyl group in the methacryloyl group with a chlorine atom. "(Meth)acrylamide" is a general term for compounds having a (meth)acryloyl group and an amide group in the molecule.

[0035] "Long-chain alkyl" means an alkyl group having 12 or more carbon atoms.

[0036] "Vinyl halide" is a compound in which at least one hydrogen atom in ethylene is replaced by a halogen atom.

[0037] The number-average molecular weight (hereinafter, also referred to as "Mn".) and the weight-average molecular weight (hereinafter, also referred to as "Mw".) of the polymer are: polystyrene-equivalent molecular weights obtained by measurement by gel permeation chromatography (hereinafter, also referred to as "GPC".) using a standard curve prepared with a standard polystyrene sample.

[0038] The solid content concentration is calculated as follows: Let the mass of the sample before heating be the sample mass, and the mass after drying the sample with a convection dryer at 120°C for 4 hours be the solid content mass, and calculate by (solid content mass / sample mass) × 100.

[0039] "~" indicating a numerical range means including the numerical values described before and after it as the lower limit value and the upper limit value.

[0040] Water Repellent Composition

[0041] The water repellent composition of the present embodiment (hereinafter, also referred to as "the present composition") contains a specific polymer (hereinafter, also referred to as "polymer (A)"). Polymer (A) is a non-fluorine polymer having a structural unit based on a (meth)acrylic acid long-chain alkyl ester monomer (hereinafter, also referred to as "monomer (a)"), a structural unit based on a vinyl halide monomer (hereinafter, also referred to as "monomer (b)"), a structural unit based on a (meth)acrylate monomer having a blocked isocyanate structure (hereinafter, also referred to as "monomer (c)"), and a structural unit based on a (meth)acrylamide monomer represented by the following formula (1) (hereinafter, also referred to as "monomer (d)"). With respect to the total amount of the structural units of polymer (A), the proportion of the structural unit based on monomer (a) is 70 to 94% by mass, the proportion of the structural unit based on monomer (b) is 5 to 20% by mass, the proportion of the unit based on monomer (c) is 0.5 to 10% by mass, and the proportion of the structural unit based on monomer (d) is 0.5 to 10% by mass. Polymer (A) may also contain either or both of the structural unit based on monomer (e) and the structural unit based on monomer (f) described later.

[0042] The present composition may also contain polymer (A) and a medium.

[0043] The present composition may also contain one or more selected from the group consisting of a surfactant, a molecular weight regulator, and a polymerization initiator.

[0044] The present composition may also contain other components as needed.

[0045] The present composition is preferably a non-fluorine polymer solution containing polymer (A). The non-fluorine polymer solution also includes a dispersion obtained by the manufacturing method described later, and a dispersion further diluted with an arbitrary medium for treating an article.

[0046] The present composition may also be a non-fluorine polymer solution containing polymer (A) and an organic solvent as a medium and not containing a surfactant.

[0047] <Polymer (A)>

[0048] Polymer (A) has: a unit based on monomer (a) (hereinafter, also referred to as "unit (a)"), a unit based on monomer (b) (hereinafter, also referred to as "unit (b)"), a unit based on monomer (c) (hereinafter, also referred to as "unit (c)"), and a unit based on monomer (d) (hereinafter, also referred to as "unit (d)").

[0049] The polymer (A) may have either or both of a unit derived from the monomer (e) (hereinafter also referred to as “unit (e)”) and a unit derived from the monomer (f) (hereinafter also referred to as “unit (f)”) as necessary.

[0050] (Monomer (a))

[0051] The monomer (a) is a long-chain alkyl (meth)acrylate monomer. The long-chain alkyl (meth)acrylate is a monomer having an alkyl group having 12 or more carbon atoms and one (meth)acryloyl group in one molecule.

[0052] As the monomer (a), a (meth)acrylic acid long-chain alkyl ester monomer represented by the following formula (2) is preferred.

[0053] R 5 -OC(=O)CR 4 =CH2 (2)

[0054] In the above formula (2), R 4 represents H, CH3 or chlorine atom, R 5 It represents an alkyl group having 12 to 30 carbon atoms.

[0055] R 4 Preferred are H or CH3, and more preferred are H.

[0056] The long-chain alkyl group may be a straight chain or a branched chain, and is preferably a straight chain.

[0057] R 5 The carbon number of the carbon fiber is preferably 12 to 30, more preferably 14 to 28, and further preferably 16 to 24. When the carbon number is at least the lower limit, the wear durability is excellent. When the carbon number is at most the upper limit, the availability and handling properties are excellent.

[0058] As the monomer (a), lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate are preferred.

[0059] In addition, two or more monomers (a) may be used in combination. As the monomer (a), it is particularly preferred that R in the above formula (2) 5 A (meth)acrylic acid long-chain alkyl ester monomer having 12 to 18 carbon atoms (hereinafter also referred to as "monomer (a1)") and R in the above formula (2) 5 A (meth)acrylic acid long-chain alkyl ester monomer having 19 to 30 carbon atoms (hereinafter, also referred to as "monomer (a2)") is used in combination.

[0060] Monomer (a1) may also be R in the above formula (2) 5A mixture of two or more of the (meth)acrylic long-chain alkyl ester monomers having 12 to 18 carbon atoms. The monomer (a2) may also be R in the aforementioned formula (2). 5 A mixture of two or more of the (meth)acrylic long-chain alkyl ester monomers having 19 to 30 carbon atoms.

[0061] The alkyl group of the monomer (a1) has 12 to 18 carbon atoms, preferably 16 to 18, more preferably 18. When the carbon number is at least the aforementioned lower limit value, the abrasion durability is excellent. When the carbon number is at most the aforementioned upper limit value, the availability and processability are excellent.

[0062] The alkyl group of the monomer (a2) has 19 to 30 carbon atoms, preferably 20 to 28, more preferably 20 to 24. When the carbon number is at least the aforementioned lower limit value, the abrasion durability is excellent. When the carbon number is at most the aforementioned upper limit value, the availability and processability are excellent.

[0063] When the monomers (a1) and (a2) are used in combination, the proportion of the structural unit based on the monomer (a1) is preferably 1 to 50% by mass, more preferably 1 to 45% by mass, still more preferably 5 to 40% by mass, and particularly preferably 10 to 38% by mass, relative to the total amount of the structural units based on the monomer (a). When the aforementioned proportion is at least the aforementioned lower limit value, the initial water repellency is better. When the aforementioned proportion is at most the aforementioned upper limit value, the abrasion durability is better.

[0064] When the monomers (a1) and (a2) are used in combination, the proportion of the structural unit based on the monomer (a2) is preferably 50 to 99% by mass, more preferably 55 to 99% by mass, still more preferably 60 to 95% by mass, and particularly preferably 62 to 90% by mass, relative to the total amount of the structural units based on the monomer (a). When the aforementioned proportion is at least the aforementioned lower limit value, the initial water repellency is better. When the aforementioned proportion is at most the aforementioned upper limit value, the abrasion durability is better.

[0065] When the monomers (a1) and (a2) are used in combination, the proportion of the structural unit based on the monomer (a1) and the structural unit based on the monomer (a2) is preferably 70% by mass or more, more preferably 72% by mass or more, still more preferably 75% by mass or more, and particularly preferably 85% by mass or more, relative to the total amount of the structural units based on the monomer (a), and may also be 100% by mass. When the aforementioned proportion is at least the aforementioned lower limit value, the initial water repellency is good. When the aforementioned proportion is at most the aforementioned upper limit value, the abrasion durability is better.

[0066] When monomers (a1) and (a2) are used in combination, the mass ratio of the structural unit based on monomer (a1) to the total amount of the structural unit based on monomer (a1) and the structural unit based on monomer (a2) is preferably 1 / 99 to 50 / 50, more preferably 1 / 99 to 45 / 55, still more preferably 5 / 95 to 40 / 60, and particularly preferably 10 / 90 to 38 / 62. When the mass ratio is at least the lower limit value, the initial water repellency is better. When the mass ratio is at most the upper limit value, the abrasion durability is better.

[0067] (Monomer (b))

[0068] Monomer (b) is a vinyl halide. By making the polymer (A) have unit (b), the adhesiveness to the treated article is improved, and the abrasion durability is improved. Furthermore, it is easy to form a dense water-repellent film on the surface of the article, and the initial water repellency is also improved. As monomer (b), a vinyl halide having one or two halogen atoms is preferred, and a vinylidene halide having two halogen atoms is more preferred.

[0069] The halogen atom of the vinyl halide is preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a chlorine atom or a bromine atom, and still more preferably a chlorine atom. In addition, when the vinyl halide has two or more halogen atoms, the plurality of halogen atoms may be the same or different.

[0070] As monomer (b), vinyl chloride or vinylidene chloride is preferred.

[0071] Two or more kinds of monomer (b) can be used in combination.

[0072] (Monomer (c))

[0073] Monomer (c) is a (meth)acrylate monomer having a blocked isocyanate structure. By making the polymer (A) have unit (c), the adhesiveness to the treated article is improved, and the abrasion durability is improved.

[0074] Having a blocked isocyanate structure means a compound having a monovalent group represented by the following formula (4).

[0075] -N(H)-C(=O)-X (4)

[0076] In the above formula (4), X represents a monovalent organic group and is a protecting group.

[0077] X is a group capable of protecting an isocyanate group.

[0078] The carbon number of X is preferably 3 to 10, more preferably 3 to 8, and still more preferably 3 to 6.

[0079] X preferably contains a heteroatom. As the heteroatom, a nitrogen atom, an oxygen atom, and a sulfur atom can be exemplified, and a nitrogen atom and an oxygen atom are preferred. The number of heteroatoms is preferably 1 to 4, more preferably 1 or 2. The atom in X bonded to the carbon atom in the aforementioned formula (4) is preferably a heteroatom, more preferably a nitrogen atom.

[0080] As X, 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 are preferred. As the oxime compound, 2-butanone oxime is preferred. As the pyrazole compound, pyrazole and a pyrazole derivative in which a hydrogen atom bonded to a carbon atom in pyrazole is substituted with an alkyl group are preferred. As the pyrazole derivative, 3-methylpyrazole and 3,5-dimethylpyrazole are preferred. As the ε-caprolactam compound, ε-caprolactam and an ε-caprolactam derivative in which a hydrogen atom bonded to a carbon atom in ε-caprolactam is substituted with an alkyl group are preferred. As X, a group in a monovalent group 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 is more preferred, and a group in a monovalent group 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 is further preferred.

[0081] The monomer (c) has one or more (meth)acryloyl groups, preferably has 1 to 6 (meth)acryloyl groups, more preferably has 1 to 4 (meth)acryloyl groups, and further preferably has 1 (meth)acryloyl group.

[0082] The monomer (c) has one or more monovalent groups represented by the aforementioned formula (4), preferably has 1 to 6 monovalent groups represented by the aforementioned formula (4), more preferably has 1 to 4 monovalent groups represented by the aforementioned formula (4), and further preferably has 1 monovalent group represented by the aforementioned formula (4). The monomer (c) may have a crosslinkable functional group described below other than the monovalent group represented by the aforementioned formula (4).

[0083] As the monomer (c), a (meth)acrylate monomer having a blocked isocyanate structure represented by the following formula (5) is preferred.

[0084] CH2=CR 6 C(=O)O-R 7 -N(H)-C(=O)-X (5)

[0085] In the aforementioned formula (5), R 6 represents H, CH3, or a chlorine atom, and R 7 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and X is the same as in the aforementioned formula (4).

[0086] R 6 Preferably H or CH3, more preferably CH3.

[0087] R 7 preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 2 carbon atoms. As R 7 The divalent hydrocarbon group of can be exemplified by a divalent saturated hydrocarbon group and a divalent unsaturated hydrocarbon group. As the divalent unsaturated hydrocarbon group, a group in which one or more carbon-carbon single bonds in the divalent saturated hydrocarbon group are replaced by a carbon-carbon double bond or a triple bond can be exemplified. R 7 is straight-chain or branched-chain, preferably straight-chain.

[0088] As R 7 preferably methylene, ethylene, propylene, trimethylene, tetramethylene, hexylene.

[0089] As the monomer (c), 2-butanone oxime adduct of 2-isocyanatoethyl (meth)acrylate ((meth)acrylic acid 2-[0-(1'-methylpropylideneamino)carboxylamino]ethyl ester), pyrazole adduct of 2-isocyanatoethyl (meth)acrylate, 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate ((meth)acrylic acid 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl ester), 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, 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 can be exemplified, preferably (meth)acrylic acid 2-[0-(1'-methylpropylideneamino)carboxylamino]ethyl ester, (meth)acrylic acid 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl ester, more preferably methylacrylic acid 2-[0-(1'-methylpropylideneamino)carboxylamino]ethyl ester, methylacrylic acid 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl ester.

[0090] Two or more kinds of the monomer (c) can be used in combination.

[0091] (Monomer (d))

[0092] The monomer (d) is a (meth)acrylamide monomer represented by the following formula (1). By making the polymer (A) have the unit (d), the adhesiveness to the article to be treated is improved, and the abrasion durability is improved.

[0093] (R 3 )2-N-R 2 -C(=O)CR 1 =CH2 (1)

[0094] In the above formula (1), R 1 represents H, CH3 or a chlorine atom, R 2 represents a single bond or a divalent organic group having 1 to 6 carbon atoms, and R 3 represents an alkyl group having 1 to 4 carbon atoms, and a plurality of Rs 3 may be the same or different optionally.

[0095] R 1 is preferably H or CH3, more preferably H.

[0096] R 2 is preferably a single bond. When R 2 is a divalent organic group, the number of carbon atoms of R 2 is preferably 1 to 4, more preferably 1 to 3, and further preferably 2 or 3.

[0097] R 2 When R 2 is a divalent organic group, R

[0098] is preferably a divalent hydrocarbon group or a divalent organic group in which one or more carbon atoms in the divalent hydrocarbon group are replaced by a heteroatom.

[0099] Examples of the divalent hydrocarbon group include a divalent saturated hydrocarbon group and a divalent unsaturated hydrocarbon group, and a divalent saturated hydrocarbon group is preferred. Examples of the divalent unsaturated hydrocarbon group include a group in which one or more carbon-carbon single bonds in the divalent saturated hydrocarbon group are replaced by a carbon-carbon double bond or a triple bond.

[0100] Examples of the divalent hydrocarbon group include methylene, ethylene, trimethylene, isopropylidene, butylene, and hexylene.

[0100] 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, and a nitrogen atom is more preferred. When R 2 contains a heteroatom, the number of heteroatoms is preferably 1 to 4, more preferably 1 to 3, and further preferably 1 or 2.

[0101] R 2 is linear or branched, and linear is preferred.

[0102] R 2 When R 2Preferably a divalent group represented by the following formula (6) or (7).

[0103] -R 8 -NH-R 8’ - Formula (6)

[0104] In the above formula (6), R 8 , R 8’ are each independently a single bond or an alkylene group having 1 to 6 carbon atoms, R 8 is bonded to the nitrogen atom in the above formula (1), and R 8’ is bonded to the carbon atom in the above formula (1). The alkylene group may be straight-chain or branched-chain, preferably straight-chain.

[0105] The carbon number of the alkylene group is preferably 1 to 4, more preferably 1 to 3, and still more preferably 2 or 3.

[0106] When R 2 is a divalent organic group, preferably in the above formula (6), R 8 is an alkylene group having 2 or 3 carbon atoms, and R 8’ is a single bond of R 2 .

[0107] -R 9 -O-R 9’ - Formula (7)

[0108] In the above formula (7), R 9 , R 9’ are each independently a single bond or an alkylene group having 1 to 6 carbon atoms, R 9 is bonded to the nitrogen atom in the above formula (1), and R 9’ is bonded to the carbon atom in the above formula (1). The alkylene group may be straight-chain or branched-chain, preferably straight-chain.

[0109] The carbon number of the alkylene group is preferably 1 to 4, more preferably 1 to 3, and still more preferably 2 or 3.

[0110] When R 2 is a divalent organic group, preferably in the above formula (7), R 9 is an alkylene group having 2 or 3 carbon atoms, and R 9’ is a single bond of R 2 .

[0111] The carbon number of R 3 is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1. Examples of R 3 include methyl, ethyl, propyl, and butyl.

[0112] Multiple R 3 are preferably the same.

[0113] As the monomer (d), examples thereof include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and preferably N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dimethylaminoethylacrylamide, N,N-dimethylaminopropylacrylamide, N,N-diethylaminoethylacrylamide, N,N-diethylaminopropylacrylamide, more preferably N,N-dimethylacrylamide, N,N-diethylacrylamide, and further preferably N,N-dimethylacrylamide.

[0114] Two or more kinds of the monomer (d) can be used in combination.

[0115] (Monomer (e))

[0116] The monomer (e) is a monomer having a crosslinkable functional group other than the monovalent group represented by the aforementioned formula (4) and one group capable of polymerizing with a (meth)acryloyl group, or a monomer having two or more groups capable of polymerizing with a (meth)acryloyl group. The monomer (e) does not have the monovalent group represented by the aforementioned formula (4).

[0117] By making the polymer (A) have a structural unit based on the monomer (e), the friction durability is further improved.

[0118] As the group capable of polymerizing with a (meth)acryloyl group, examples thereof include a group having a carbon-carbon double bond at the molecular terminal, for example, preferably a (meth)acryloyl group, a vinyl group, or an allyl group.

[0119] As the crosslinkable functional group, preferably a functional group having at least one of a covalent bond, an ionic bond, or a hydrogen bond, or a functional group capable of forming a crosslinked structure through the interaction of the aforementioned bonds.

[0120] As the aforementioned functional group, preferably an 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, a sulfonic acid group, etc., and particularly preferably a hydroxyl group, a primary amino group, or an epoxy group.

[0121] As the monomer (e), preferably (meth)acrylates having a crosslinkable functional group other than the monomer (a) and the monomer (c), acrylamides other than the monomer (d), vinyl ethers having a crosslinkable functional group, or vinyl esters having a crosslinkable functional group. As the monomer (e), the following compounds can be cited.

[0122] 2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate.

[0123] Methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, butoxymethyl (meth)acrylamide, diacetone acrylamide, γ-methacryloyloxypropyltrimethoxysilane, trimethoxyvinylsilane, vinyltrimethoxysilane.

[0124] Tert-butyl (meth)acrylamidosulfonic acid, (meth)acrylamide, N-hydroxymethyl (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)acryloyloxyhexahydrophthalate, 2-(meth)acryloyloxyethyl acid phosphate, allyl (meth)acrylate, 2-vinyl-2-oxazoline, polycaprolactone of 2-vinyl-4-methyl-(2-vinyloxazoline) hydroxyethyl (meth)acrylate.

[0125] Tri(meta)allyl isocyanurate (T(M)AIC, manufactured by Nippon Kayaku Co., Ltd.), triallyl cyanurate (TAC, manufactured by Nippon Kayaku Co., Ltd.), 3-(methyl ethyl ketoxime) isocyanatomethyl-3,5,5-trimethylcyclohexyl (2-hydroxyethyl methacrylate) cyanate (Tech Coat HE-6P, manufactured by Kyokuen Kasei Co., Ltd.). Polycaprolactone of 2-hydroxyethyl (meth)acrylate (Placcel FA, FM series, manufactured by Daicel Chemical Industries, Ltd.).

[0126] As monomer (e), N-hydroxymethyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, 3-chloro-2-hydroxypropyl methacrylate or polycaprolactone of 2-hydroxyethyl (meth)acrylate (Placcel FA, FM series, manufactured by Daicel Chemical Industries, Ltd.) is preferred.

[0127] (Monomer (f))

[0128] Monomer (f) is a monomer other than monomer (a), monomer (b), monomer (c), monomer (d), and monomer (e).

[0129] As monomer (f), the following compounds can be cited.

[0130] Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-hexyl (meth)acrylate, benzyl (meth)acrylate, octyl (meth)acrylate, decyl methacrylate, cyclododecyl acrylate, 3-ethoxypropyl acrylate, methoxy-butyl acrylate, 2-ethylbutyl acrylate, 1,3-dimethylbutyl acrylate, 2-methylpentyl acrylate.

[0131] Vinyl acetate, vinyl propionate, butene, isoprene, butadiene, ethylene, propylene, vinyl ethylene, pentene, ethyl-2-propene, butyl ethylene, cyclohexylpropyl ethylene, decyl ethylene, dodecyl ethylene, hexene, isohexyl ethylene, neopentyl ethylene, (1,2-diethoxycarbonyl)ethylene, (1,2-dipropoxycarbonyl)ethylene, methoxyethylene, ethoxyethylene, butoxyethylene, 2-methoxypropylene, pentyloxyethylene, cyclopentyloxycarbonylethylene, cyclopentylacetoxyethylene, styrene, α-methylstyrene, p-methylstyrene, hexylstyrene, octylstyrene, nonylstyrene.

[0132] N-methyl(meth)acrylamide, (meth)acryloxyethyltrimethylammonium chloride, (meth)acryloxypropyltrimethylammonium chloride, (meth)acrylamideethyltrimethylammonium chloride, (meth)acrylamidepropyltrimethylammonium chloride, (meth)acryloylmorpholine.

[0133] Vinyl alkyl ether, haloalkyl vinyl ether, vinyl alkyl ketone, aziridinylethyl (meth)acrylate, 2-ethylhexyl polyoxyalkylene (meth)acrylate, polyoxyalkylene di(meth)acrylate.

[0134] Alkyl crotonate, alkyl maleate, alkyl fumarate, alkyl citraconate, alkyl mesaconate, triallyl cyanurate, allyl acetate, N-vinylcarbazole, maleimide, N-methylmaleimide, (meth)acrylate with an organosilicon in the side chain, (meth)acrylate with a urethane, (meth)acrylate with a polyoxyalkylene chain having an alkyl with 1 to 4 carbon atoms at the end, alkylene di(meth)acrylate.

[0135] Relative to all the units constituting polymer (A), the total proportion of unit (a), unit (b), unit (c), and unit (d) is preferably 80% by mass or more, more preferably 80 - 99% by mass, and still more preferably 82 - 98% by mass. When the total proportion of unit (a), unit (b), unit (c), and unit (d) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent.

[0136] When the polymer (A) contains either or both of the unit (e) and the unit (f), the total proportion of the unit (a), the unit (b), the unit (c), and the unit (d) is preferably 80% by mass or more, more preferably 85 to 98% by mass, and further preferably 90 to 98% by mass, based on all the units constituting the polymer (A).

[0137] The proportion of the unit (a) is 70 to 94% by mass, preferably 72 to 92% by mass, and more preferably 74 to 90% by mass, based on the total amount of the structural units of the polymer (A). The proportion of the unit (a) is preferably 70 to 94% by mass, more preferably 72 to 92% by mass, further preferably 72 to 90% by mass, and particularly preferably 74 to 88% by mass, based on the total amount of the unit (a), the unit (b), the unit (c), and the unit (d). When the proportion of the unit (a) is not less than the above lower limit value, the abrasion durability of the article treated with the present composition is more excellent. When the proportion of the unit (a) is not more than the above upper limit value, the unit (b), the unit (c), the unit (d), and other units can be sufficiently contained, and the abrasion durability of the article treated with the present composition is more excellent.

[0138] The proportion of the unit (b) is 5 to 20% by mass, preferably 6 to 15% by mass, and more preferably 6 to 12% by mass, based on the total amount of the structural units of the polymer (A). The proportion of the unit (b) is preferably 5 to 20% by mass, more preferably 6 to 18% by mass, further preferably 6 to 16% by mass, and particularly preferably 6 to 12% by mass, based on the total amount of the unit (a), the unit (b), the unit (c), and the unit (d). When the proportion of the unit (b) is not less than the above lower limit value, the abrasion durability of the article treated with the present composition is more excellent. When the proportion of the unit (b) is not more than the above upper limit value, the unit (a), the unit (c), the unit (d), and other units can be sufficiently contained, and the abrasion durability of the article treated with the present composition is more excellent.

[0139] The proportion of the unit (c) is 0.5 to 10% by mass, preferably 0.6 to 8% by mass, and more preferably 0.8 to 6% by mass, based on the total amount of the structural units of the polymer (A). The proportion of the unit (c) is preferably 0.5 to 10% by mass, more preferably 0.8 to 8% by mass, and further preferably 1 to 7% by mass, based on the total amount of the unit (a), the unit (b), the unit (c), and the unit (d). When the proportion of the unit (c) is not less than the above lower limit value, the abrasion durability of the article treated with the present composition is more excellent. When the proportion of the unit (c) is not more than the above upper limit value, the unit (a), the unit (b), the unit (d), and other units can be sufficiently contained, and the abrasion durability of the article treated with the present composition is more excellent.

[0140] The proportion of unit (d) is 0.5 to 10% by mass, preferably 0.6 to 8% by mass, more preferably 0.8 to 6% by mass, relative to the total amount of the structural units of polymer (A). The proportion of unit (d) is preferably 0.5 to 10% by mass, more preferably 0.8 to 8% by mass, still more preferably 1 to 7% by mass, relative to the total amount of units (a), (b), (c), and (d). When the proportion of unit (d) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the proportion of unit (d) is at most the above upper limit value, units (a), (b), (c), and other units can be sufficiently contained, and the abrasion durability of the article treated with this composition is more excellent.

[0141] The total proportion of units (a) and (b) is preferably 80% by mass or more, more preferably 85 to 99% by mass, still more preferably 87 to 98% by mass, relative to the total amount of the structural units of polymer (A). When the total proportion of units (a) and (b) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the proportion of units (a) and (b) is at most the above upper limit value, units (c), (d), and other units can be sufficiently contained, and the abrasion durability of the article treated with this composition is more excellent.

[0142] The total proportion of units (c) and (d) is preferably 0.1 to 15% by mass, more preferably 0.5 to 12% by mass, still more preferably 1.0 to 10% by mass, relative to the total amount of the structural units of polymer (A). When the total proportion of units (c) and (d) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the proportion of units (c) and (d) is at most the above upper limit value, units (a), (b), and other units can be sufficiently contained, and the abrasion durability of the article treated with this composition is more excellent.

[0143] The total proportion of units (b), (c), and (d) is preferably 1 to 35% by mass, more preferably 3 to 30% by mass, still more preferably 5 to 28% by mass, relative to the total amount of the structural units of polymer (A). When the total proportion of units (b), (c), and (d) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the proportion of units (b), (c), and (d) is at most the above upper limit value, unit (a) and other units can be sufficiently contained, and the abrasion durability of the article treated with this composition is more excellent.

[0144] The mass ratio of unit (a) / unit (b) is preferably 1.0 to 15.0, more preferably 2.0 to 12.0, and further preferably 3.0 to 10.0. When the mass ratio of unit (a) / unit (b) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the mass ratio of unit (a) / unit (b) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0145] The mass ratio of unit (a) / unit (c) is preferably 5.0 to 120, more preferably 8.0 to 110, and further preferably 10.0 to 100. When the mass ratio of unit (a) / unit (c) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the mass ratio of unit (a) / unit (c) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0146] The mass ratio of unit (a) / unit (d) is preferably 5.0 to 120, more preferably 8.0 to 110, and further preferably 10.0 to 100. When the mass ratio of unit (a) / unit (d) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the mass ratio of unit (a) / unit (d) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0147] The mass ratio of unit (b) / unit (c) is preferably 1.0 to 15.0, more preferably 1.2 to 13.0, and further preferably 1.5 to 11.0. When the mass ratio of unit (b) / unit (c) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the mass ratio of unit (b) / unit (c) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0148] The mass ratio of unit (b) / unit (d) is preferably 1.0 to 15.0, more preferably 1.2 to 13.0, and further preferably 1.5 to 11.0. When the mass ratio of unit (b) / unit (d) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the mass ratio of unit (b) / unit (d) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0149] The mass ratio of unit (c) / unit (d) is preferably from 0.05 to 10.0, more preferably from 0.1 to 8.0, and still more preferably from 0.2 to 6.0. When the mass ratio of unit (c) / unit (d) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the mass ratio of unit (c) / unit (d) is at most the above upper limit value, the polymerization of the monomer components is likely to proceed during the production of polymer (A).

[0150] The mass ratio of {unit (a) + unit (b)} / {unit (c) + unit (d)} is preferably from 1.0 to 60.0, more preferably from 1.5 to 55.0, and still more preferably from 2.0 to 50.0. When the mass ratio of {unit (a) + unit (b)} / {unit (c) + unit (d)} is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the mass ratio of {unit (a) + unit (b)} / {unit (c) + unit (d)} is at most the above upper limit value, the polymerization of the monomer components is likely to proceed during the production of polymer (A).

[0151] When polymer (A) contains unit (e), the proportion of unit (e) relative to the total amount of the structural units of polymer (A) is preferably from 0.1 to 10% by mass, more preferably from 0.4 to 8% by mass, and still more preferably from 0.5 to 6% by mass. When the proportion of unit (e) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the proportion of unit (e) is at most the above upper limit value, units (a), (b), (c), (d), and other units can be sufficiently contained, and the abrasion durability of the article treated with this composition is more excellent.

[0152] When polymer (A) contains unit (f), the proportion of unit (f) relative to the total amount of the structural units of polymer (A) is preferably from 0.1 to 10% by mass, more preferably from 0.4 to 8% by mass, and still more preferably from 0.5 to 6% by mass. When the proportion of unit (f) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the proportion of unit (f) is at most the above upper limit value, units (a), (b), (c), (d), and other units can be sufficiently contained, and the abrasion durability of the article treated with this composition is more excellent.

[0153] When the polymer (A) contains the unit (e) or the unit (f), the total proportion of the unit (e) and the unit (f) is preferably 0.1 to 10% by mass, more preferably 0.4 to 8% by mass, and still more preferably 0.5 to 6% by mass, based on the total amount of the structural units of the polymer (A). When the proportion of the unit (e) and the unit (f) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the proportion of the unit (e) and the unit (f) is at most the above upper limit value, the units (a), (b), (c), and (d) can be sufficiently contained, and the abrasion durability of the article treated with this composition is more excellent.

[0154] The proportion of each unit can be calculated by the reaction rate of each monomer component obtained by using 1 1H-NMR, gas chromatography, and high performance liquid chromatography. When the conversion rate of the monomer component to the polymer (A) is high (for example, 90% or more) during the production of the polymer (A), the proportion of each unit can also be calculated based on the input amount of the monomer component.

[0155] The Mn of the polymer (A) is preferably 5,000 to 1,000,000, more preferably 10,000 to 900,000, and still more preferably 20,000 to 800,000. When the Mn of the polymer (A) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the Mn of the polymer (A) is at most the above upper limit value, the water dispersibility of the polymer (A) is more excellent.

[0156] The Mw of the polymer (A) is preferably 8,000 to 3,000,000, more preferably 16,000 to 2,800,000, and still more preferably 32,000 to 2,400,000. When the Mw of the polymer (A) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the Mw of the polymer (A) is at most the above upper limit value, the water dispersibility of the polymer (A) is more excellent.

[0157] (medium)

[0158] Examples of the medium include water, alcohol, glycol, glycol ether, halogen compound, hydrocarbon, ketone, ester, ether, nitrogen compound, sulfur compound, inorganic solvent, organic acid, etc. Among them, from the viewpoints of solubility and ease of treatment, it is preferable to select one or more media selected from the group consisting of water, alcohol, glycol, glycol ether, and glycol ester.

[0159] As the alcohol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1,1-dimethylethanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1,1-dimethylpropanol, 3-methyl-2-butanol, 1,2-dimethylpropanol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, etc. can be cited.

[0160] As the diol or diol ether, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, polypropylene glycol, hexylene glycol, etc. can be cited.

[0161] As the halogen compound, halogenated hydrocarbon, halogenated ether, etc. can be cited. The halogen compound preferably does not contain fluorine. As the halogenated hydrocarbon, hydrochlorofluorocarbon, hydrobromofluorocarbon, etc. can be cited.

[0162] As the hydrocarbon, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, etc. can be cited.

[0163] As the aliphatic hydrocarbon, pentane, 2-methylbutane, 3-methylpentane, hexane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, decane, undecane, dodecane, 2,2,4,6,6-pentamethylheptane, tridecane, tetradecane, hexadecane, etc. can be cited.

[0164] As the alicyclic hydrocarbon, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. can be cited.

[0165] As the aromatic hydrocarbon, benzene, toluene, xylene, etc. can be cited.

[0166] As the ketone, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, etc. can be cited.

[0167] As the ester, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, methyl lactate, ethyl lactate, pentyl lactate, etc. can be cited.

[0168] As the ether, diisopropyl ether, dioxane, tetrahydrofuran, etc. can be cited.

[0169] As the nitrogen compound, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can be cited.

[0170] Examples of the sulfur compound include dimethyl sulfoxide and sulfolane.

[0171] Examples of the inorganic solvent include liquid carbon dioxide.

[0172] Examples of the organic acid include acetic acid, propionic acid, malic acid, and lactic acid.

[0173] One type of the medium can be used alone, or two or more types can be used in combination. When two or more types of the medium are used in combination, it is preferably used in combination with water. By using the mixed medium, it is easy to control the solubility and dispersibility of the polymer, and it is easy to control the permeability, wettability, solvent drying rate, etc. of the article during processing.

[0174] When the medium is a mixture of an organic solvent and water, the content of the organic solvent is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, and further preferably 3 to 25 parts by mass relative to 100 parts by mass of water.

[0175] (Surfactant)

[0176] Examples of the surfactant include hydrocarbon surfactants. Examples of the hydrocarbon surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, or amphoteric surfactants.

[0177] As the surfactant, from the aspect of dispersion stability, a combination use of a nonionic surfactant and a cationic surfactant or an amphoteric surfactant, or a single anionic surfactant is preferred, and a combination use of a nonionic surfactant and a cationic surfactant is preferred.

[0178] The mass ratio of the nonionic surfactant to the cationic surfactant is preferably 97 / 3 to 40 / 60.

[0179] For a specific combination of a nonionic surfactant and a cationic surfactant, the total amount relative to the polymer (A) (100% by mass) can be 5% by mass or less, and thus the adverse effect on the water repellency of the article can be reduced.

[0180] As the nonionic surfactant, it is preferably at least one selected from the group consisting of surfactants s 1 ~s 6 constituting the group.

[0181] Surfactant s 1 :

[0182] Surfactant s 1It is polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, or polyoxyalkylene monoalkapolyenyl ether.

[0183] As surfactant s 1 , preferably polyoxyalkylene monoalkyl ether or polyoxyalkylene monoalkenyl ether. Surfactant s 1 can be used alone in one kind or two or more kinds can be used in combination.

[0184] As alkyl, alkenyl, or alkapolyenyl (hereinafter, alkyl, alkenyl, and alkapolyenyl are collectively referred to as R s group).), preferably a group having 4 to 26 carbon atoms. R s group can be straight-chain or branched-chain. As the branched-chain R s group, preferably secondary alkyl, secondary alkenyl or secondary alkapolyenyl.

[0185] As R s group, specific examples include octyl, dodecyl, tetradecyl, hexadecyl, stearyl (octadecyl), behenyl (docosyl), oleyl (9-octadecenyl), etc.

[0186] As the polyoxyalkylene (hereinafter referred to as POA.) chain, preferably any one or both of the polyoxyethylene (hereinafter referred to as POE.) chain and the polyoxypropylene (hereinafter referred to as POP.) chain connected by two or more. The POA chain can be a chain containing one kind of POA chain or a chain containing two or more kinds of POA chains. In the case of containing two or more kinds of POA chains, each POA chain is preferably connected in a block form.

[0187] As surfactant s 1 , more preferably compound (s 11 ).

[0188] R 10 O[CH2CH(CH3)O] s -(CH2CH2O) r H···(s 11 ).

[0189] Among them, R 10 is an alkyl group having 8 or more carbon atoms or an alkenyl group having 8 or more carbon atoms, r is an integer of 5 to 50, and s is an integer of 0 to 20.

[0190] When r is 5 or more, it is soluble in water and uniformly dissolved in the aqueous medium, so the water repellent composition has good permeability to the article. When r is 50 or less, hydrophilicity can be inhibited and water repellency is good.

[0191] When s is less than 20, it is soluble in water and uniformly dissolved in an aqueous medium. Therefore, the water repellent composition has good permeability to the article.

[0192] When r and s are 2 or more, the POE chain and the POP chain are connected in a block form.

[0193] As R 10 , a straight chain or a branched chain is preferred.

[0194] r is preferably an integer of 10 to 30.

[0195] s is preferably an integer of 0 to 10.

[0196] As the compound (s 11 ), the following compounds can be mentioned. Among them, the POE chain and the POP chain are connected in a block form.

[0197] C 18 H 37 O[CH2CH(CH3)O]2-(CH2CH2O) 30 H,

[0198] C 18 H 35 O-(CH2CH2O) 30 H,

[0199] C 16 H 33 O[CH2CH(CH3)O]5-(CH2CH2O) 20 H,

[0200] C 12 H 25 O[CH2CH(CH3)O]2-(CH2CH2O) 15 H,

[0201] (C8H 17 )(C6H 13 )CHO-(CH2CH2O) 15 H,

[0202] C 10 H 21 O[CH2CH(CH3)O]2-(CH2CH2O) 15 H.

[0203] The surfactant s 2 :

[0204] The surfactant s 2 is a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in the molecule.

[0205] As the surfactant s2 , preferably a compound having 1 carbon-carbon triple bond and 1 or 2 hydroxyl groups in the molecule.

[0206] Surfactant s 2 It may have a POA chain in the molecule. As the POA chain, a POE chain, a POP chain, a chain in which a POE chain and a POP chain are connected randomly, or a chain in which a POE chain and a POP chain are connected in blocks can be cited.

[0207] As surfactant s 2 , preferably compound (s 21 ) to (s 24 ).

[0208] HO-C(R 11 )(R 12 )-C≡C-C(R 13 )(R 14 )-OH ··· (s 21 ),

[0209] HO-(A 1 O) u -C(R 11 )(R 12 )-C≡C-C(R 13 )(R 14 )-(OA 2 ) v -OH ··· (s 22 ),

[0210] HO-C(R 15 )(R 16 )-C≡C-H ··· (s 23 ),

[0211] HO-(A 3 O) w -C(R 15 )(R 16 )-C≡C-H ··· (s 24 ).

[0212] A 1 to A 3 are each an alkylene group.

[0213] u and v are each an integer of 0 or more, and (u + v) is an integer of 1 or more.

[0214] w is an integer of 1 or more.

[0215] When u, v, and w are each 2 or more, A 1 to A 3 may be the same or different from each other.

[0216] As the POA chain, a POE chain, a POP chain, or a chain containing a POE chain and a POP chain is preferred. The number of repeating units of the POA chain is preferably 1 to 50.

[0217] R 11 ~R 16 Each is a hydrogen atom or an alkyl group.

[0218] As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group.

[0219] As the compound(s 22 )), the compound(s 25 ) is preferred.

[0220]

[0221] Among them, x and y are each an integer of 0 to 100.

[0222] The compound(s 25 ) can be used alone or in combination of two or more.

[0223] As the compound(s 25 ), a compound in which x and y are 0, a compound in which the average of the sum of x and y is 1 to 4, or a compound in which the average of the sum of x and y is 10 to 30 is preferred.

[0224] Surfactant s 3 :

[0225] Surfactant s 3 is a compound in which two or more oxyalkylene groups having 3 or more carbon atoms are continuously connected, a POA chain and a POE chain are connected, and both ends are hydroxyl groups.

[0226] As the aforementioned POA chain, either or both of polyoxytetramethylene (hereinafter referred to as POT.) and POP chain are preferred.

[0227] As surfactant s 3 , the compound(s 31 ) or the compound(s 32 ) is preferred.

[0228] HO(CH2CH2O) g1 (C3H6O) t (CH2CH2O) g2 H···(s 31 ),

[0229] HO(CH2CH2O) g1(CH2CH2CH2CH2O) t (CH2CH2O) g2 H···(s 32 )。

[0230] g1 is an integer from 0 to 200.

[0231] t is an integer from 2 to 100.

[0232] g2 is an integer from 0 to 200.

[0233] When g1 is 0, g2 is an integer of 2 or more. When g2 is 0, g1 is an integer of 2 or more.

[0234] -C3H6- can be -CH(CH3)CH2-, can be -CH2CH(CH3)-, or can be a mixture of -CH(CH3)CH2- and -CH2CH(CH3)-.

[0235] The POA chain is block-shaped.

[0236] As the surfactant s 3 , the following compounds can be cited.

[0237] HO-(CH2CH2O) 15 -(C3H6O) 35 -(CH2CH2O) 15 H,

[0238] HO-(CH2CH2O)8-(C3H6O) 35 -(CH2CH2O)8H,

[0239] HO-(CH2CH2O) 45 -(C3H6O) 17 -(CH2CH2O) 45 H,

[0240] HO-(CH2CH2O) 34 -(CH2CH2CH2CH2O) 28 -(CH2CH2O) 34 H.

[0241] The surfactant s 4 :

[0242] The surfactant s 4 is a compound having an amine oxide moiety in the molecule.

[0243] As the surfactant s 4 , the compound (s 41 ) is preferred.

[0244] (R 17 )(R 18 )(R 19 )N(→O)···(s 41 )。

[0245] R 17 ~R 19 Each is a monovalent hydrocarbon group.

[0246] In this specification, a surfactant having an amine oxide (N→O) is regarded as a nonionic surfactant.

[0247] Compound (s 41 ) can be used alone or in combination of two or more.

[0248] As compound (s 41 ), from the aspect of the dispersion stability of the polymer, compound (s 42 ) is preferred.

[0249] (R 20 )(CH3)2N(→O)···(s 42 )。

[0250] R 20 is an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, a phenyl group bonded with an alkyl group having 6 to 22 carbon atoms, or a phenyl group bonded with an alkenyl group having 6 to 22 carbon atoms. As R 20 , an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms is preferred.

[0251] As compound (s 42 ), the following compounds can be cited.

[0252] [H(CH2) 12 (CH3)2N(→O),

[0253] [H(CH2) 14 (CH3)2N(→O),

[0254] [H(CH2) 16 (CH3)2N(→O),

[0255] [H(CH2) 18 (CH3)2N(→O).

[0256] Surfactant s 5 :

[0257] Surfactant s 5 is a condensate of polyoxyethylene mono(substituted phenyl) ether or polyoxyethylene mono(substituted phenyl) ether.

[0258] As the substituted phenyl group, a phenyl group substituted with a monovalent hydrocarbon group is preferred, and a phenyl group substituted with an alkyl group, an alkenyl group or a styryl group is more preferred.

[0259] As surfactant s 5 , condensates of polyoxyethylene mono(alkylphenyl) ethers, condensates of polyoxyethylene mono(alkenylphenyl) ethers, polyoxyethylene mono(alkylphenyl) ethers, polyoxyethylene mono(alkenylphenyl) ethers, or polyoxyethylene mono[(alkyl)(styryl)phenyl] ethers are preferred.

[0260] As the condensate of polyoxyethylene mono(substituted phenyl) ether or polyoxyethylene mono(substituted phenyl) ether, formaldehyde condensates of polyoxyethylene mono(nonylphenyl) ether, polyoxyethylene mono(nonylphenyl) ether, polyoxyethylene mono(octylphenyl) ether, polyoxyethylene mono(oleylphenyl) ether, polyoxyethylene mono[(nonyl)(styryl)phenyl] ether, polyoxyethylene mono[(oleyl)(styryl)phenyl] ether, etc. can be cited.

[0261] Surfactant s 6 :

[0262] Surfactant s 6 is a fatty acid ester of a polyol.

[0263] The polyol represents glycerol, sorbitan, sorbitol, polyglycerol, polyethylene glycol, polyoxyethylene glycerol ether, polyoxyethylene sorbitan ether or polyoxyethylene sorbitol ether.

[0264] As surfactant s 6 , 1:1 (molar ratio) ester of stearic acid and polyethylene glycol, 1:4 (molar ratio) ester of sorbitol and ether of polyethylene glycol with oleic acid, 1:1 (molar ratio) ester of polyoxyethylene and ether of sorbitan with stearic acid, 1:1 (molar ratio) ester of polyethylene glycol and ether of sorbitan with oleic acid, 1:1 (molar ratio) ester of dodecanoic acid and sorbitan, 1:1 or 2:1 (molar ratio) ester of oleic acid and decaglycerol, 1:1 or 2:1 (molar ratio) ester of stearic acid and decaglycerol can be cited.

[0265] Surfactant s 7 :

[0266] When the surfactant contains a cationic surfactant, as the aforementioned cationic surfactant, surfactant s is preferred 7 .

[0267] Surfactant s 7 is a substituted ammonium salt.

[0268] As surfactant s 7, preferably an ammonium salt in which one or more of the hydrogen atoms bonded to the nitrogen atom are substituted with an alkyl group, an alkenyl group, or a POA chain having a hydroxyl group at the end, more preferably the compound (s 71 ).

[0269] [(R 21 )4N + ·X - ···(s 71 ).

[0270] R 21 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a POA chain having a hydroxyl group at the end. The four Rs 21 are optionally the same or different, provided that the four Rs 21 are not all hydrogen atoms at the same time.

[0271] As R 21 , preferably a long-chain alkyl group having 6 to 22 carbon atoms, or a long-chain alkenyl group having 6 to 22 carbon atoms.

[0272] R 21 is an alkyl group other than a long-chain alkyl group, as R 21 , preferably methyl or ethyl.

[0273] R 21 is a POA chain having a hydroxyl group at the end, as the POA chain, preferably a POE chain.

[0274] X - is a counter ion.

[0275] As X - , preferably chloride ion, ethyl sulfate ion, or acetate ion.

[0276] As the compound (s 71 ), examples include stearyl trimethyl ammonium chloride, stearyl dimethyl monoethyl ammonium ethyl sulfate, mono(stearyl)monomethyl di(polyethylene glycol) ammonium chloride, monofluorohexyl trimethyl ammonium chloride, di(tallow alkyl) dimethyl ammonium chloride, dimethyl mono coconut amine acetate, etc.

[0277] Surfactant s 8 :

[0278] When the surfactant contains an amphoteric surfactant, as the aforementioned amphoteric surfactant, preferably surfactant s 8 .

[0279] Surfactant s 8 is alanine type, imidazolium betaine type, amide betaine type or acetic acid betaine.

[0280] As surfactant s 8The hydrophobic group it has is preferably a long-chain alkyl group having 6 to 22 carbon atoms or a long-chain alkenyl group having 6 to 22 carbon atoms.

[0281] As surfactant s 8 , examples thereof include dodecyl betaine, stearyl betaine, dodecyl carboxymethyl hydroxyethyl imidazolium betaine, dodecyl dimethylaminoacetic acid betaine, fatty acid amide propyl dimethylaminoacetic acid betaine, etc.

[0282] Surfactant s 9 :

[0283] As the surfactant, surfactant s 9 can be used.

[0284] Surfactant s 9 is a polymer surfactant composed of a block copolymer, random copolymer of a hydrophilic monomer and a hydrocarbon-based hydrophobic monomer, or a hydrophobic modified product of a hydrophilic copolymer.

[0285] As surfactant s 9 , examples thereof include block or random copolymers of polyethylene glycol (meth)acrylate and long-chain alkyl acrylate, block or random copolymers of vinyl acetate and long-chain alkyl vinyl ether, block or random copolymers of vinyl acetate and long-chain alkyl vinyl ester, polymers of styrene and maleic anhydride, condensates of polyvinyl alcohol and stearic acid, condensates of polyvinyl alcohol and stearyl mercaptan, condensates of polyallylamine and stearic acid, condensates of polyethyleneimine and stearyl alcohol, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, etc.

[0286] As surfactant s 9 Commercially available products thereof include MP polymers (product numbers: MP-103, MP-203) from Kuraray Co., Ltd., SMA resin from Elf Atochem, METOLOSE from Shin-Etsu Chemical Co., Ltd., EPOMIN RP from Nippon Shokubai Co., Ltd., etc.

[0287] As a combination of surfactants, from the aspects of excellent water repellency and durability of the water repellent composition and the stability of the obtained emulsion, surfactant s 1 and surfactant s 2 and surfactant s 7 combination, or surfactant s 1 and surfactant s 3 and surfactant s 7 combination, or surfactant s 1 and surfactant s 2 and surfactant s 3 and surfactant s7 in combination, more preferably surfactant s 7 is the above combination of compound (s 71 ). The total amount of the surfactant is preferably 1 to 10 parts by mass, more preferably 1 to 7 parts by mass, relative to 100 parts by mass of the polymer.

[0288] (Molecular weight regulator)

[0289] As the molecular weight regulator, for example, aromatic compounds, mercapto alcohols, mercapto carboxylic acids, and alkyl mercaptans are preferred, and mercapto carboxylic acids or alkyl mercaptans are more preferred. As the molecular weight regulator, for example, mercaptoethanol, mercaptopropionic acid, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, stearyl mercaptan, α-methylstyrene dimer (CH2=C(Ph)CH2C(CH3)2Ph, where Ph is a phenyl group), and n-dodecyl mercaptan, tert-dodecyl mercaptan, and stearyl mercaptan are particularly preferred.

[0290] (Polymerization initiator)

[0291] As the polymerization initiator, for example, thermal polymerization initiators, photo polymerization initiators, radiation polymerization initiators, radical polymerization initiators, and ionic polymerization initiators can be mentioned, and radical polymerization initiators are preferred. As the radical polymerization initiator, for example, according to the polymerization temperature, azo-based polymerization initiators, peroxide-based polymerization initiators, and redox initiators can be used. As the radical polymerization initiator, azo-based compounds are preferred, and salts of azo-based compounds are more preferred. As the initiator, for example, acetate of 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (manufactured by Wako Pure Chemical Industries, Ltd., VA-061), 2,2'-azobis(2-amidinopropane) (manufactured by Nippon Kayaku Co., Ltd., NC-32) can be mentioned. The polymerization temperature is preferably 30 to 80 °C.

[0292] (Other components)

[0293] The water repellent composition of this embodiment may further contain other components as needed.

[0294] As other components, crosslinking agents, penetrants, defoamers, water absorbents, antistatic agents, antistatic polymers, wrinkle-proofing agents, handle modifiers, film-forming aids, water-soluble polymers (such as polyacrylamide, polyvinyl alcohol, etc.), thermosetting agents (such as melamine resins, urethane resins, compounds containing a triazine ring, isocyanate-based compounds, etc.), epoxy curing agents (such as isophthalic dihydrazide, adipic dihydrazide, sebacic dihydrazide, dodecanedioic dihydrazide, 1,6-hexamethylenebis(N,N-dimethyl semicarbazide), 1,1,1',1'-tetramethyl-4,4'-(methylenedi-p-phenylene) diaminourea, spirodiol, etc.), thermosetting catalysts, crosslinking catalysts, synthetic resins, fiber stabilizers, inorganic fine particles, etc. can be cited.

[0295] The water repellent composition of the present embodiment may contain, as needed, polymers other than the polymer (A) of the present embodiment that can exhibit water repellency, commercially available water repellents, water repellent compounds without fluorine atoms, etc. As the water repellent compounds without fluorine atoms, paraffin-based compounds, aliphatic amide-based compounds, alkylethyleneurea compounds, silicon-based compounds, etc. can be cited.

[0296] When the composition contains a crosslinking agent, the adhesion to the substrate is likely to be improved.

[0297] As the crosslinking agent, isocyanate-based crosslinking agents, hydroxymethyl-based crosslinking agents, carbodiimide-based crosslinking agents, and oxazoline-based crosslinking agents are preferred.

[0298] As the isocyanate-based crosslinking agent, an isocyanate-based crosslinking agent having two or more isocyanate groups is preferred.

[0299] As the isocyanate-based crosslinking agent, for example, aromatic-capped isocyanate-based crosslinking agents, aliphatic-capped isocyanate-based crosslinking agents, aromatic non-capped isocyanate-based crosslinking agents, aliphatic non-capped isocyanate-based crosslinking agents can be cited. The isocyanate-based crosslinking agent is preferably a water-dispersed type emulsified with a surfactant or a self-water-dispersed type having a hydrophilic group.

[0300] As the hydroxymethyl-based crosslinking agent, for example, condensates or pre-condensates of urea or melamine with formaldehyde, hydroxymethyl-dihydroxyethylene-urea and its derivatives, hydroxymethyl-ethylene-urea, hydroxymethyl-propylene-urea, hydroxymethyl-triazole, condensates of dicyandiamide-formaldehyde, hydroxymethyl-carbamate, hydroxymethyl-(meth)acrylamide, and their polymers can be cited.

[0301] The carbodiimide-based crosslinking agent is a polymer having a carbodiimide group in the molecule and is a crosslinking agent that shows excellent reactivity with carboxyl groups, amino groups, and active hydrogen groups of articles, etc.

[0302] The oxazoline-based crosslinking agent is a polymer having an oxazoline group in the molecule and is a crosslinking agent that exhibits excellent reactivity with the carboxyl group of an article or the like.

[0303] As other crosslinking agents, for example, divinyl sulfone, polyamide and its cationic derivatives, polyamine and its cationic derivatives, epoxy derivatives such as diglycidyl glycerol, halogenated derivatives such as (epoxy-2,3-propyl)trimethylammonium chloride and N-methyl-N-(epoxy-2,3-propyl)morpholinium chloride, pyridinium salt of chloromethyl ether of ethylene glycol, polyamine-polyamide-epichlorohydrin resin, polyvinyl alcohol or its derivatives, polyacrylamide or its derivatives, and glyoxal resin-based anti-wrinkle agents can be cited.

[0304] When this composition contains a hydroxymethyl-based crosslinking agent or a glyoxal resin-based anti-wrinkle agent, as an additive, a catalyst is preferably contained. As preferred catalysts, for example, inorganic amine salts and organic amine salts can be cited. As inorganic amine salts, for example, ammonium chloride can be cited. As organic amine salts, for example, amino alcohol hydrochloride and semicarbazide hydrochloride can be cited. As amino alcohol hydrochloride, for example, monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanol hydrochloride, and 2-amino-2-methylpropanol hydrochloride can be cited.

[0305] (Ratio of each component)

[0306] When this composition contains a medium, the content of the medium can be appropriately selected according to the desired solid content concentration of this composition.

[0307] The solid content concentration of this composition is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 45% by mass immediately after manufacturing this composition.

[0308] Regarding the solid content concentration of this composition, when this composition is used for treating an article, it is preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.5 to 8% by mass.

[0309] It should be noted that the solid content concentration is the total content of the polymer (A) and the surfactant in this composition.

[0310] The ratio of the polymer (A) to the total mass of this composition is preferably 0.01 to 60% by mass, more preferably 0.1 to 50% by mass, and further preferably 0.5 to 45% by mass.

[0311] When this composition contains a surfactant, the content of the surfactant in this composition is preferably 1 to 10 parts by mass, more preferably 1 to 8 parts by mass, and further preferably 2 to 7 parts by mass with respect to 100 parts by mass of the polymer (A).

[0312] When the composition contains a molecular weight regulator, the content of the molecular weight regulator in the composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 9 parts by mass, and still more preferably 1 to 8 parts by mass with respect to 100 parts by mass of the polymer (A).

[0313] When the composition contains a polymerization initiator, the content of the polymerization initiator in the composition is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and still more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the polymer (A).

[0314] The content of fluorine atoms is preferably 0.1% by mass or less, more preferably 0% by mass, relative to the total mass of the composition. The content of fluorine atoms relative to the total mass of the composition can be measured by combustion ion chromatography or the like.

[0315] "Method for Producing Non-Fluorine Polymer"

[0316] The method for producing a non-fluorine polymer according to this embodiment is the following production method: In the presence of a surfactant and a polymerization initiator, a mixture containing monomer components is polymerized, and the monomer components include monomer (a), monomer (b), monomer (c), and monomer (d) represented by the following formula (3). The proportion of monomer (a) is 70 to 94% by mass, the proportion of monomer (b) is 5 to 20% by mass, the proportion of monomer (c) is 0.5 to 10% by mass, and the proportion of monomer (d) is 0.5 to 10% by mass with respect to the total mass of all the monomers constituting the non-fluorine polymer. In addition, a water repellent composition is also produced.

[0317] (R 3’ )2-N-R 2’ -C(=O)CR 1’ =CH2 (3)

[0318] In the above formula (3), R1’ represents H, CH3, or a chlorine atom, R 2’ represents a single bond or a divalent organic group having 1 to 6 carbon atoms, R 3’ represents an alkyl group having 1 to 4 carbon atoms, and multiple Rs 3’ are optionally the same or different. R 1’ , R 2’ , R 3’ are each the same as R 1 , R 2 , R 3 in the above formula (1).

[0319] The monomer components may further contain either or both of monomer (e) and monomer (f).

[0320] Monomer (a), monomer (b), monomer (c), monomer (d), monomer (e), and monomer (f) can each be a substance produced by a known production method. For commercially available monomers, commercially available products can be used.

[0321] With respect to the total mass of the monomers constituting the non-fluoropolymer, the total proportion of monomer (a), monomer (b), monomer (c), and monomer (d) contained in the mixture is preferably 80% by mass or more, more preferably 80 to 99% by mass, and still more preferably 82 to 98% by mass. When the total proportion of monomer (a), monomer (b), monomer (c), and monomer (d) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent.

[0322] When the monomer component contains either or both of monomer (e) and monomer (f), with respect to the total mass of the monomers constituting the non-fluoropolymer, the total proportion of monomer (a), monomer (b), monomer (c), and monomer (d) contained in the mixture is preferably 80% by mass or more, more preferably 85 to 98% by mass, and still more preferably 90 to 98% by mass.

[0323] With respect to the total mass of the monomers constituting the non-fluoropolymer, the proportion of monomer (a) contained in the mixture is 70 to 94% by mass, preferably 72 to 92% by mass, and more preferably 74 to 90% by mass. With respect to the total mass of monomer (a), monomer (b), monomer (c), and monomer (d) constituting the non-fluoropolymer, the proportion of monomer (a) is preferably 70 to 94% by mass, more preferably 72 to 92% by mass, and still more preferably 72 to 90% by mass. When the proportion of monomer (a) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the proportion of monomer (a) is at most the above upper limit value, monomer (b), monomer (c), and monomer (d) can be sufficiently contained, and the abrasion durability of the article treated with this composition is more excellent.

[0324] With respect to the total mass of the monomers constituting the non-fluoropolymer, the proportion of monomer (b) contained in the mixture is 5 to 20% by mass, preferably 6 to 15% by mass, and more preferably 6 to 12% by mass. With respect to the total mass of monomer (a), monomer (b), monomer (c), and monomer (d) constituting the non-fluoropolymer, the proportion of monomer (b) is preferably 5 to 20% by mass, more preferably 6 to 18% by mass, still more preferably 6 to 16% by mass, and particularly preferably 6 to 12% by mass. When the proportion of monomer (b) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the proportion of monomer (b) is at most the above upper limit value, monomer (a), monomer (c), and monomer (d) can be sufficiently contained, and the abrasion durability of the article treated with this composition is more excellent.

[0325] The proportion of monomer (c) contained in the mixture is 0.5 to 10% by mass, preferably 0.6 to 8% by mass, more preferably 0.8 to 6% by mass, relative to the total mass of the monomers constituting the non-fluoropolymer. The proportion of monomer (c) is preferably 0.5 to 10% by mass, more preferably 0.8 to 8% by mass, and further preferably 1 to 7% by mass, relative to the total mass of monomers (a), (b), (c), and (d) constituting the non-fluoropolymer. When the proportion of monomer (c) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the proportion of monomer (c) is at most the above upper limit value, monomers (a), (b), and (d) can be sufficiently contained, and the abrasion durability of the article treated with this composition is more excellent.

[0326] The proportion of monomer (d) contained in the mixture is 0.5 to 10% by mass, preferably 0.6 to 8% by mass, more preferably 0.8 to 6% by mass, relative to the total mass of the monomers constituting the non-fluoropolymer. The proportion of monomer (d) is preferably 0.5 to 10% by mass, more preferably 0.8 to 8% by mass, and further preferably 1 to 7% by mass, relative to the total mass of monomers (a), (b), (c), and (d) constituting the non-fluoropolymer. When the proportion of monomer (d) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the proportion of monomer (d) is at most the above upper limit value, monomers (a), (b), and (c) can be sufficiently contained, and the abrasion durability of the article treated with this composition is more excellent.

[0327] The total proportion of monomers (a) and (b) contained in the mixture is preferably 80% by mass or more, more preferably 85 to 99% by mass, and further preferably 87 to 98% by mass, relative to the total mass of the monomers constituting the non-fluoropolymer. When the total proportion of monomers (a) and (b) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the total proportion of monomers (a) and (b) is at most the above upper limit value, monomers (c) and (d) can be sufficiently contained, and the abrasion durability of the article treated with this composition is more excellent.

[0328] The total proportion of monomers (c) and (d) contained in the mixture is preferably 0.1 to 15% by mass, more preferably 0.5 to 12% by mass, and further preferably 1 to 10% by mass, relative to the total mass of the monomers constituting the non-fluoropolymer. When the total proportion of monomers (c) and (d) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the total proportion of monomers (c) and (d) is at most the above upper limit value, monomers (a) and (b) can be sufficiently contained, and the abrasion durability of the article treated with this composition is more excellent.

[0329] With respect to the total mass of the monomers constituting the non-fluorine polymer, the total proportion of monomers (b), (c), and (d) contained in the mixture is preferably 1 to 35% by mass, more preferably 3 to 30% by mass, and still more preferably 5 to 28% by mass. When the total proportion of monomers (b), (c), and (d) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the total proportion of monomers (b), (c), and (d) is at most the above upper limit value, monomer (a) can be sufficiently contained, and the abrasion durability of the article treated with this composition is more excellent.

[0330] The mass ratio of monomer (a) / monomer (b) contained in the mixture is preferably 1.0 to 15.0, more preferably 2.0 to 12.0, and still more preferably 3.0 to 10.0. When the mass ratio of monomer (a) / monomer (b) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the mass ratio of monomer (a) / monomer (b) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0331] The mass ratio of monomer (a) / monomer (c) contained in the mixture is preferably 5.0 to 120, more preferably 8.0 to 110, and still more preferably 10.0 to 100. When the mass ratio of monomer (a) / monomer (c) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the mass ratio of monomer (a) / monomer (c) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0332] The mass ratio of monomer (a) / monomer (d) contained in the mixture is preferably 5.0 to 120, more preferably 8.0 to 110, and still more preferably 10.0 to 100. When the mass ratio of monomer (a) / monomer (d) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the mass ratio of monomer (a) / monomer (d) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0333] The mass ratio of monomer (b) / monomer (c) contained in the mixture is preferably 1.0 to 15.0, more preferably 1.2 to 13.0, and still more preferably 1.5 to 11.0. When the mass ratio of monomer (b) / monomer (c) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the mass ratio of monomer (b) / monomer (c) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0334] The mass ratio of monomer (b) / monomer (d) contained in the mixture is preferably 1.0 to 15.0, more preferably 1.2 to 13.0, and still more preferably 1.5 to 11.0. When the mass ratio of monomer (b) / monomer (d) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the mass ratio of monomer (b) / monomer (d) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0335] The mass ratio of monomer (c) / monomer (d) contained in the mixture is preferably 0.05 to 10.0, more preferably 0.1 to 8.0, and still more preferably 0.2 to 6.0. When the mass ratio of monomer (c) / monomer (d) is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the mass ratio of monomer (c) / monomer (d) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0336] The mass ratio of {monomer (a) + monomer (b)} / {monomer (c) + monomer (d)} contained in the mixture is preferably 1.0 to 60.0, more preferably 1.5 to 55.0, and still more preferably 2.0 to 50.0. When the mass ratio of {monomer (a) + monomer (b)} / {monomer (c) + monomer (d)} is at least the above lower limit value, the abrasion durability of the article treated with this composition is more excellent. When the mass ratio of {monomer (a) + monomer (b)} / {monomer (c) + monomer (d)} is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0337] When the mixture contains monomer (e), the proportion of monomer (e) is preferably 0.1 to 10% by mass, more preferably 0.4 to 8% by mass, and still more preferably 0.5 to 6% by mass relative to the total mass of the monomers constituting the non-fluoropolymer.

[0338] When the mixture contains monomer (f), the proportion of monomer (f) is preferably 0.1 to 10% by mass, more preferably 0.4 to 8% by mass, and still more preferably 0.5 to 6% by mass relative to the total mass of the monomers constituting the non-fluoropolymer.

[0339] When the mixture contains monomer (e) or monomer (f), the total proportion of monomer (e) and monomer (f) contained in the mixture is preferably 0.1 to 10% by mass, more preferably 0.4 to 8% by mass, and still more preferably 0.5 to 6% by mass relative to the total mass of the monomers constituting the non-fluoropolymer.

[0340] As a polymerization method of monomer components, emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method, etc. can be mentioned. Among these, the emulsion polymerization method is preferred. By polymerizing the monomer components by the emulsion polymerization method, the molecular weight (Mn, Mw) of the polymer (A) can be increased.

[0341] In the emulsion polymerization method, for example, the aforementioned monomer components are polymerized in an emulsion containing a medium, monomer components, a surfactant, and a polymerization initiator. The emulsion may contain a molecular weight regulator as needed.

[0342] Examples of the medium, surfactant, polymerization initiator, and molecular weight regulator are the same as those mentioned above.

[0343] Relative to 100 parts by mass of all monomers constituting the non-fluoropolymer, the proportion of the aforementioned molecular weight regulator is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.1 to 5 parts by mass.

[0344] The emulsion can be prepared by mixing the medium, monomer components, and surfactant as needed, dispersing them with a homogenizer, high-pressure emulsifier, etc., and then adding the polymerization initiator. It should be noted that when the monomer component is a gas, it can be added to the reaction system after the aforementioned dispersion.

[0345] The concentration of the monomer components in the emulsion is preferably 5 to 60% by mass, more preferably 10 to 50% by mass. When the concentration of the monomer components in the emulsion is within the aforementioned range, the molecular weight of the polymer (A) can be sufficiently increased.

[0346] The content of the surfactant in the emulsion is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the monomer components. When the content of the surfactant is above the aforementioned lower limit value, the dispersion stability of the emulsion is excellent. When the content of the surfactant is below the aforementioned upper limit value, the adverse effect on the water repellency of the article treated with the composition containing the polymer (A) caused by the surfactant can be reduced.

[0347] The content of the polymerization initiator in the emulsion is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the monomer components. When the content of the polymerization initiator is above the aforementioned lower limit value, the reaction rate is likely to be high and the polymerization yield is likely to be increased. When the content of the polymerization initiator is below the aforementioned upper limit value, a polymer with a molecular weight in the desired range is easily obtained.

[0348] By polymerizing the monomer components in the emulsion, a dispersion of the polymer (A) is obtained.

[0349] In the dispersion, the polymer (A) is dispersed in the aqueous medium in the form of emulsion particles.

[0350] In the dispersion liquid, the average particle diameter of the emulsified particles of polymer (A) is preferably 10 to 1000 nm, more preferably 30 to 600 nm, and still more preferably 50 to 300 nm. When the average particle diameter is at or below the aforementioned upper limit value, the water repellency of the article treated with the emulsified particles of polymer (A) and the dispersibility of the emulsified particles of polymer (A) are more excellent. When the average particle diameter is at or above the aforementioned lower limit value, the emulsified particles of polymer (A) are more stable to mechanical shear force.

[0351] Regarding the average particle diameter of the emulsified particles of polymer (A), it is calculated by analyzing the autocorrelation function obtained by dynamic light scattering method for a sample in which the dispersion liquid of polymer (A) is diluted with water to a solid content concentration of 1% by mass, by the cumulant method.

[0352] The dispersion liquid of polymer (A) obtained by polymerizing the monomer components in the emulsion can be used directly as this composition, or can be diluted with an aqueous medium to adjust the solid content concentration and then used as this composition. Other components can also be added to this composition.

[0353] <Treatment method of water repellent composition>

[0354] The treatment method of this embodiment is a treatment method using this composition. Any method that can attach this composition to the article to be treated can be used. For example, when this composition contains a liquid medium, methods such as coating, infiltration, dipping, spraying, brushing, filling, sizing press, and rollers can be cited. After treating the article with this dispersion liquid by a known method, it is dried.

[0355] The amount of the solid component in the water repellent composition attached to the article to be treated is not particularly limited. For example, in the case of a fiber fabric, it is preferably 0.1 to 5 g per 100 g of the fiber fabric.

[0356] The amount of polymer (A) in the water repellent composition attached to the article to be treated is not particularly limited. For example, in the case of a fiber fabric, it is preferably 0.05 to 5 g per 100 g of the fiber fabric.

[0357] Drying can be carried out at room temperature or by heating, and heating is preferred. In the case of heating, the heating temperature is preferably 90 to 200 °C, more preferably 110 to 190 °C, and still more preferably 120 to 180 °C. In addition, when the water repellent composition contains a crosslinking agent, if necessary, it is preferably heated to above the crosslinking temperature of the aforementioned crosslinking agent for curing.

[0358] <Article>

[0359] The article of this embodiment is an article treated with this composition.

[0360] Examples of the article to be treated with the present composition include fibers, fibrous fabrics (woven fabrics, knitted fabrics, non-woven fabrics, fleece fabrics, etc.), fiber products having fibrous fabrics (clothing materials such as ski suits, raincoats, coats, jackets, windbreakers, down jackets, sportswear, work clothes, uniforms, protective clothing, etc., backpacks, bags, tents, etc.), glass, paper, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded products, and porous resins. The porous resin can be used as a filter, for example. Examples of the material of the porous resin include polypropylene, polyethylene terephthalate, and polytetrafluoroethylene.

[0361] As the article to be treated, fibers, fibrous fabrics, and fiber products having fibrous fabrics are preferred. The type of fiber is not particularly limited, and examples include natural fibers such as cotton, wool, silk, or cellulose, chemical fibers such as polyester, polyamide, acrylic, aramid, rayon, or Lyocell, and fibers obtained by using a plurality of these fibers. Examples of the fiber in the case where the fiber substrate is a non-woven fabric include polyethylene, polypropylene, polyolefin, polyethylene terephthalate, polytetrafluoroethylene, glass, and rayon.

[0362] The thickness of the fibrous fabric is not particularly limited and is 10 μm to 5 cm.

[0363] (Mechanism of action)

[0364] For the present composition described above, since the polymer (A) has specific amounts of the units (a), (b), (c), and (d) respectively, the abrasion durability of the article treated with the present composition is excellent. It is considered that particularly by having both the specific amounts of the units (c) and (d), the abrasion durability of the article treated with the present composition is excellent. As shown in the examples described later, when only having a specific amount of the unit (c) and not having the unit (d), or when only having a specific amount of the unit (d) and not having the unit (c), the abrasion durability of the treated article is poor. Furthermore, even when having both the units (c) and (d), if the amounts of the units (c) and (d) are less than the specific amounts, the abrasion durability of the treated article is also poor. It is considered that due to the synergistic effect brought about by having both the specific amounts of the units (c) and (d), the adhesiveness to the article is improved.

[0365] Examples

[0366] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these. Examples 1 to 10 are examples, and Examples 11 to 36 are comparative examples.

[0367] <Ratio of monomer units>

[0368] The composition of the polymer (the ratio of each monomer unit to all the units constituting the polymer) is calculated based on the input amounts of the monomer components.

[0369] <Water-repellent treatment of fabric>

[0370] The emulsion obtained in the following examples was diluted with distilled water, and after adjusting the solid content concentration to 1.0% by mass, a blocked isocyanate (MEIKANATE TP-10 manufactured by Meisei Chemical Industry Co., Ltd.) as a crosslinking agent was added so that the concentration became 1.0% by mass as an auxiliary agent for combined use, and a water-repellent agent composition was prepared. The dyed PET fabric was immersed in this water-repellent agent composition, and squeezed so that the content of the water-repellent agent composition relative to the total mass of the water-repellent agent composition and the dyed PET fabric became 60% by mass. After drying it at 110 °C for 90 seconds, it was further heat-treated at 170 °C for 60 seconds to obtain a test fabric.

[0371] <Water-repellency evaluation: Measurement of water contact angle (initial)>

[0372] A glass plate was placed under the test fabric, and about 2 μL of distilled water was dropped onto the surface of the test fabric. The contact angle of the above-mentioned distilled water was measured using a contact angle measuring device DM-500 (manufactured by Kyowa Interface Science Co., Ltd.). The measurement was carried out at three different positions on the surface of the test fabric, and their average value was calculated. The contact angle was calculated using the 2θ method.

[0373] <Abrasion durability evaluation: Measurement of water contact angle (after abrasion)>

[0374] For the test fabric, after applying a load of 1 kg with a new Martindale friction tester and performing 2500 abrasions, it was left overnight or more, and the contact angle was measured by the same method as above.

[0375] The value obtained by subtracting the contact angle after friction from the initial contact angle is shown in the "Δ" column of Tables 1 to 3.

[0376] The compound names described in this specification are as follows.

[0377] Monomer (a):

[0378] BeA: Behenyl acrylate

[0379] StA: Stearyl acrylate

[0380] Monomer (b):

[0381] VdCl: Vinylidene chloride

[0382] VCM: Vinyl chloride

[0383] Monomer (c):

[0384] MOI-BP: 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate

[0385] Monomer (d):

[0386] DMAA: N,N-dimethylacrylamide

[0387] Monomer (e)

[0388] NMAM: N-hydroxymethylacrylamide

[0389] HEMA: 2-hydroxyethyl methacrylate

[0390] Surfactant:

[0391] E420: Polyoxyethylene oleyl ether (Emulgen (trade name of Kao Corporation) 420, about 13 moles of ethylene oxide adduct)

[0392] P204: 10 mass% aqueous solution of ethylene oxide-propylene oxide polymer (trade name of NOF Corporation, Plonon 204, 40 mass% of ethylene oxide)

[0393] AQ-18-63: Solution of 63% stearyl trimethyl ammonium chloride, 32% isopropyl alcohol, and 5% water (manufactured by LION SPECIALTY CHEMICALS CO., Ltd.)

[0394] PEO-20: 10 mass% aqueous solution of polyoxyethylene oleyl ether (manufactured by Kao Chemical, E430, about 26 moles of ethylene oxide adduct)

[0395] SFY465: 10 mass% aqueous solution of 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethylene oxide adduct (SURFYNOL 465 of Nissin Chemical Industry Co., Ltd., 10 moles of ethylene oxide adduct)

[0396] Molecular weight regulator:

[0397] n-DOSH: n-dodecyl mercaptan

[0398] StSH: stearyl mercaptan

[0399] Polymerization initiator:

[0400] VA-061A: 10 mass% aqueous solution of acetate of 2,2’-azobis[2-(2-imidazolin-2-yl)propane] (manufactured by Wako Pure Chemical Industries, Ltd., VA-061)

[0401] Medium:

[0402] DPG: Dipropylene glycol

[0403] Water

[0404] (Example 1)

[0405] <Manufacture of Polymer Emulsion>

[0406] In a glass beaker, 29.2 g of StA, 58.2 g of BeA, 1.0 g of MOI-BP, 1.0 g of DMAA, 1.0 g of n-DoSH, 2.5 g of E420, 0.5 g of P204, 0.5 g of AQ-18-63, 30.9 g of DPG, and 155 g of water were placed. After heating at 60 °C for 30 minutes, a homogeneous mixer (manufactured by Nippon Seiki Co., Ltd., BioMixer) was used for mixing to obtain a mixed solution.

[0407] While maintaining the above mixed solution at 60 °C, it was treated at 40 MPa using a high-pressure emulsifier (manufactured by APV Rannie Co., Ltd., Mini Labo) to obtain an emulsion. The emulsion was placed in a stainless-steel reactor and cooled to 40 °C or lower. 0.5 g of VA-061A was added, the gas phase was replaced with nitrogen, and then 9.6 g of VCM was introduced. While stirring, a polymerization reaction was carried out at 60 °C for 15 hours to obtain a polymer emulsion. Using the obtained emulsion, the water contact angle measurement (initial) and the water contact angle measurement (after abrasion) were performed. The results are shown in Table 1 (hereinafter, the results of Examples 2 to 36 are also shown in Tables 1 to 3).

[0408] (Examples 2 to 5, 9 to 20, 24 to 36)

[0409] Using the monomers (a) to (e), surfactants, molecular weight regulators, polymerization initiators, and media shown in Tables 1 to 3, and changing the input ratios shown in Tables 1 to 3, the operations were the same as in Example 1 except for this, to obtain a polymer emulsion. It should be noted that monomer (e) was added at the time of adding monomer (a), monomer (c), and monomer (d). The input ratios in Tables 1 to 3 are in parts by mass. Using the obtained emulsion, the water contact angle measurement (initial) and the water contact angle measurement (after abrasion) were performed.

[0410] (Example 6)

[0411] In a glass beaker, 28.8 g of StA, 57.6 g of BeA, 2.0 g of MOI-BP, 2.0 g of DMAA, 1.0 g of StSH, 2.5 g of E420, 0.5 g of P204, 0.5 g of AQ-18-63, 30 g of DPG, and 155 g of water were placed. After heating at 60 °C for 30 minutes, a homogeneous mixer (manufactured by Nippon Seiki Co., Ltd., BioMixer) was used for mixing to obtain a mixed solution.

[0412] The emulsion was obtained by treating the above-mentioned mixed solution at 60°C with a high-pressure emulsifier (manufactured by APV Rannie Co., Ltd., Mini Labo) at 40 MPa. The emulsion was placed in a stainless steel reactor and cooled to 40°C or lower. Then, 9.6 g of VdCl was added, 0.5 g of VA-061A was added, the gas phase was replaced with nitrogen, and a polymerization reaction was carried out at 60°C for 15 hours with stirring to obtain a polymer emulsion. Using the obtained emulsion, the water contact angle measurement (initial) and the water contact angle measurement (after abrasion) were carried out.

[0413] (Examples 7, 8, 21 to 23)

[0414] Using the monomers (a) to (e), surfactant, molecular weight regulator, polymerization initiator, and medium shown in Tables 1 and 2, and changing the input ratio shown in Tables 1 and 2, the operation was carried out in the same manner as in Example 6 to obtain a polymer emulsion. It should be noted that monomer (e) was added at the time of adding monomers (a), (c), and (d). Using the obtained emulsion, the water contact angle measurement (initial) and the water contact angle measurement (after abrasion) were carried out.

[0415] [Table 1]

[0416]

[0417] [Table 2]

[0418]

[0419] [Table 3]

[0420]

[0421] Examples 1 to 10 using specific amounts of monomers (a), (b), (c), and (d) have high abrasion durability. Examples 12 to 14, 21, 24, 27, 30, 33 to 36 that do not use monomers (c) and (d) have low abrasion durability. In addition, Examples 15 to 20, 22, 23, 25, 26, 28, 29, 31, 32 that do not use either of monomers (c) and (d) all have low abrasion durability. Furthermore, even in the case where monomers (a), (b), (c), and (d) are used, Example 11 with a small amount of monomers (c) and (d) used also has low abrasion durability.

Claims

1. A water repellent composition comprising a non-fluoropolymer having a structural unit based on a (meth)acrylic acid long-chain alkyl ester monomer, a structural unit based on a vinyl halide monomer, a structural unit based on a (meth)acrylate monomer having a blocked isocyanate structure, and a structural unit based on a (meth)acrylamide monomer represented by the following formula (1). With respect to the total amount of the structural units of the non-fluoropolymer, the proportion of the structural unit based on the (meth)acrylic acid long-chain alkyl ester monomer is 70 to 94% by mass, the proportion of the structural unit based on the vinyl halide monomer is 5 to 20% by mass, the proportion of the unit based on the (meth)acrylate monomer having a blocked isocyanate structure is 0.5 to 10% by mass, and the proportion of the structural unit based on the (meth)acrylamide monomer is 0.5 to 10% by mass. (R 3 )2-N-R 2 -C(=O)CR 1 =CH2 (1) In the formula (1), R 1 represents H, CH3 or a chlorine atom, R 2 represents a single bond or a divalent organic group having 1 to 6 carbon atoms, R 3 represents an alkyl group having 1 to 4 carbon atoms, and multiple Rs 3 are optionally the same or different.

2. The water repellent composition according to claim 1, wherein, The (meth)acrylic acid long-chain alkyl ester monomer is represented by the following formula (2). R 5 -OC(=O)CR 4 =CH2 (2) In the formula (2), R 4 represents H, CH3 or a chlorine atom, and R 5 represents an alkyl group having 12 to 30 carbon atoms.

3. The water repellent composition according to claim 2, wherein, The structural unit based on the (meth)acrylic acid long-chain alkyl ester monomer contains R in the formula (2) 5 The structural unit of the (meth)acrylic acid long-chain alkyl ester monomer with 12 to 18 carbon atoms based on R in the formula (2) and R in the formula (2) 5 The structural unit of the (meth)acrylic acid long-chain alkyl ester monomer with 19 to 30 carbon atoms.

4. The water repellent composition according to claim 3, wherein, Based on the total amount of the structural units of the (meth)acrylic acid long-chain alkyl ester monomer, the proportion of the structural units of the (meth)acrylic acid long-chain alkyl ester monomer having 19 to 30 carbon atoms represented by R in the formula (2) is 50 to 99% by mass. 5 ​ 5. The water repellent composition according to claim 1, wherein The vinyl halide monomer is vinyl chloride or vinylidene chloride.

6. The water repellent composition according to claim 1, wherein, The (meth)acrylate monomer having a blocked isocyanate structure is 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate or 2-[0-(1'-methylpropylideneamino)carboxylamino]ethyl methacrylate.

7. The water repellent composition according to claim 1, wherein, The (meth)acrylamide monomer is at least one monomer selected from the group consisting of N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dimethylaminoethylacrylamide, N,N-dimethylaminopropylacrylamide, N,N-diethylaminoethylacrylamide, and N,N-diethylaminopropylacrylamide.

8. A method for manufacturing a non-fluorinated polymer, which polymerizes a mixture containing a (meth)acrylic long-chain alkyl ester monomer, a vinyl halide monomer, a (meth)acrylate monomer having a blocked isocyanate structure, and a (meth)acrylamide monomer represented by the following formula (3) in the presence of a surfactant and a polymerization initiator, wherein, Based on the total mass of all the monomers constituting the non-fluorine polymer, the proportion of the (meth)acrylic long-chain alkyl ester monomer is 70 to 94% by mass, the proportion of the vinyl halide monomer is 5 to 20% by mass, the proportion of the (meth)acrylate monomer having a blocked isocyanate structure is 0.5 to 10% by mass, and the proportion of the (meth)acrylamide monomer is 0.5 to 10% by mass, (R 3’ )2-N-R 2’ -C(=O)CR 1’ =CH2 (3) In the formula (3), R 1’ represents H, CH3 or a chlorine atom, R 2’ represents a single bond or a divalent organic group having 1 to 6 carbon atoms, R 3’ represents an alkyl group having 1 to 4 carbon atoms, and multiple R 3’ are optionally the same or different.

9. A treatment method using the water repellent composition according to any one of claims 1 to 7.

10. An article treated with the water repellent composition according to any one of claims 1 to 7.

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