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

Abstract

The present invention relates to a water repellent composition containing a non-fluoropolymer having a structural unit based on a long-chain alkyl (meth) acrylate monomer, a structural unit based on a halogenated ethylene monomer, and a structural unit based on a monomer having two or more (meth) acryloyl groups.

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. 2022-186728 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 by not having a polyfluoroalkyl group, having 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: WO2009 / 113589 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] However, articles treated with the water repellent composition containing the copolymer described in Patent Document 1 sometimes do not have sufficient water repellency.

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

[0011] Means for Solving the Problems

[0012] The present invention has the following embodiments.

[0013] [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, and a structural unit based on a monomer having two or more (meth)acryloyl groups.

[0014] [2] The water repellent composition according to [1], wherein the (meth)acrylic acid long-chain alkyl ester monomer is represented by the following formula (1).

[0015] R 2 -OC(=O)CR 1 =CH2 (1)

[0016] In the above formula (1), R 1 represents H, CH3 or a chlorine atom, preferably H or CH3, more preferably H, and R 2 represents an alkyl group having 12 to 30, 14 to 28, or 16 to 24 carbon atoms.

[0017] [3] The water repellent composition according to [2], wherein the structural unit based on the (meth)acrylic acid long-chain alkyl ester monomer includes a structural unit based on a (meth)acrylic acid long-chain alkyl ester monomer having 12 to 18, 16 to 18, or 18 carbon atoms in R in the above formula (1) and a structural unit based on a (meth)acrylic acid long-chain alkyl ester monomer having 19 to 30, 20 to 28, or 20 to 24 carbon atoms in R in the above formula (1). 2 2

[0018] [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 based on a (meth)acrylic acid long-chain alkyl ester monomer having 12 to 18, 16 to 18, or 18 carbon atoms in R in the above formula (1) is 1 to 45% by mass, 5 to 40% by mass, or 10 to 38% by mass. 2

[0019] [5] The water repellent composition according to any one of [1] to [4], wherein the vinyl halide monomer is vinyl chloride or vinylidene chloride.

[0020] [6] The water repellent composition according to any one of [1] to [5], wherein the monomer having two or more (meth)acryloyl groups is represented by the following formula (2).

[0021] Q-(R 4 C(=O)CR 3 =CH2)n (2)

[0022]

[0023] In the foregoing formula (2), n represents an integer of 2 to 10, R 3 represents H, CH3 or a chlorine atom, R 4 represents a single bond or a divalent organic group, Q represents a linear or branched alkylene group having 1 to 16 carbon atoms, a residue obtained by removing hydrogen from a hydroxyl group of a polyol, a trivalent group represented by the foregoing formula (3), or a trivalent group represented by the foregoing formula (4), and a plurality of (R 4 C(=O)CR 3 =CH2) may be the same or different. In the foregoing formula (3) and the foregoing formula (4), * represents a bonding site. Among them, when Q is a linear or branched alkylene group having 1 to 16 carbon atoms or a residue obtained by removing hydrogen from a hydroxyl group of a polyol, the atom in R 4 bonded to Q is an atom other than an oxygen atom.

[0024] [7] The water repellent composition according to any one of [1] to [6], wherein, based on the total amount of the structural units of the foregoing non-fluoropolymer, the proportion of the structural units based on the (meth)acrylic long-chain alkyl ester monomer is 50 to 90% by mass, 55 to 90% by mass, or 60 to 85% by mass, the proportion of the structural units based on the vinyl halide monomer is 5 to 30% by mass, 5 to 25% by mass, or 8 to 20% by mass, and the proportion of the structural units based on the monomer having two or more (meth)acryloyl groups is 0.1 to 20% by mass, 0.5 to 15% by mass, or 1 to 10% by mass.

[0025] [8] A method for producing a non-fluoropolymer, which polymerizes a mixture containing a (meth)acrylic long-chain alkyl ester monomer, a vinyl halide monomer, and a monomer having two or more (meth)acryloyl groups in the presence of a surfactant and a polymerization initiator, wherein, based on the total mass of the monomers constituting the foregoing non-fluoropolymer, the proportion of the (meth)acrylic long-chain alkyl ester monomer is 50 to 90% by mass, 55 to 90% by mass, or 60 to 85% by mass, the proportion of the vinyl halide monomer is 5 to 30% by mass, 5 to 25% by mass, or 8 to 20% by mass, and the proportion of the monomer having two or more (meth)acryloyl groups is 0.1 to 20% by mass, 0.5 to 15% by mass, or 1 to 10% by mass.

[0026] [9] The method for producing a non-fluoropolymer according to [8], wherein, further, the polymerization is carried out in the presence of a molecular weight regulator.

[0027]

[10] The method for producing a non-fluoropolymer according to [9], wherein the proportion of the molecular weight regulator is 0.1 to 20 parts by mass, 0.1 to 10 parts by mass, 0.5 to 9 parts by mass, or 1 to 8 parts by mass relative to 100 parts by mass of all the monomers constituting the non-fluoropolymer.

[0028]

[11] A treatment method that uses the water repellent composition according to any one of [1] to [7].

[0029]

[12] An article obtained by treating with the water repellent composition according to any one of [1] to [7].

[0030] Effects of the Invention

[0031] According to the present invention, it is possible to provide a water repellent composition capable of obtaining an article with more excellent water repellency, a method for producing a non-fluoropolymer, a treatment method using the water repellent composition, and an article with excellent water repellency obtained by treating with the water repellent composition. Detailed Description

[0032] The meanings and definitions of the terms in this specification are as follows.

[0033] "Non-fluoropolymer" is a general term for polymers in which the content of fluorine atoms relative to the total mass of the polymer is 0.1% by mass or less. The content of fluorine atoms relative to the total mass of the polymer can be measured by combustion ion chromatography or the like.

[0034] "Structural unit based on monomer" is a general term for atomic groups directly formed by polymerization of one molecule of monomer and atomic groups obtained by chemically converting a part of the atomic groups.

[0035] "(Meth)acrylate" is a general term for acrylate, methacrylate, and compounds obtained by replacing the methyl group in the methacryloyl group of the methacrylate with a chlorine atom. Similarly, "(meth)acryloyl" is a general term for acryloyl, methacryloyl, and groups obtained by replacing the methyl group in the methacryloyl group with a chlorine atom.

[0036] "Long-chain alkyl" refers to an alkyl group having 12 or more carbon atoms.

[0037] "Vinyl halide" is a compound in which at least one hydrogen atom in ethylene is replaced by a halogen atom.

[0038] 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 the 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.

[0039] The solid component concentration is calculated as follows: The mass of the sample before heating is defined as the sample mass, and the mass of the sample after drying for 4 hours using a convection dryer at 120°C is defined as the solid component mass. It is calculated by (solid component mass / sample mass) × 100.

[0040] The "~" indicating a numerical range means including the numerical values described before and after it as the lower limit value and the upper limit value.

[0041] Water - repellent agent composition

[0042] The water - repellent agent composition of the present embodiment (hereinafter, also referred to as "this 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)".), and a structural unit based on a monomer having two or more (meth) acryloyl groups (hereinafter, also referred to as "monomer (c)".). Polymer (A) may also contain any one or both of the structural unit based on monomer (d) and the structural unit based on monomer (e) described later.

[0043] This composition may also contain polymer (A) and a medium.

[0044] This composition may also contain one or more selected from the group consisting of a surfactant, a molecular weight regulator, and a polymerization initiator.

[0045] This composition may also contain other components as needed.

[0046] This 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.

[0047] This composition may also be a non - fluorine polymer solution containing polymer (A) and an organic solvent as a medium and not containing a surfactant.

[0048] <Polymer (A)>

[0049] 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)".), and a unit based on monomer (c) (hereinafter, also referred to as "unit (c)".).

[0050] The polymer (A) may also have, as needed, either or both of a unit based on the monomer (d) (hereinafter also referred to as "unit (d)") and a unit based on the monomer (e) (hereinafter also referred to as "unit (e)").

[0051] (Monomer (a))

[0052] The monomer (a) is a (meth)acrylic long-chain alkyl ester monomer. The (meth)acrylic long-chain alkyl ester is a monomer having an alkyl group with 12 or more carbon atoms and one (meth)acryloyl group in one molecule.

[0053] As the monomer (a), a (meth)acrylic long-chain alkyl ester monomer represented by the following formula (1) is preferred.

[0054] R 2 -OC(=O)CR 1 =CH2 (1)

[0055] In the above formula (1), R 1 represents H, CH3 or a chlorine atom, and R 2 represents an alkyl group having 12 to 30 carbon atoms.

[0056] R 1 is preferably H or CH3, more preferably H.

[0057] The long-chain alkyl group may be linear or branched, preferably linear.

[0058] R 2 The carbon number of 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 value, the water repellency is excellent. When the carbon number is at most the upper limit value, the availability and processability are excellent.

[0059] As the monomer (a), lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate are preferred.

[0060] In addition, two or more kinds of the monomer (a) can be used in combination. As the monomer (a), a (meth)acrylic long-chain alkyl ester monomer having 12 to 18 carbon atoms in R 2 in the above formula (1) (hereinafter also referred to as "monomer (a1)") and a (meth)acrylic long-chain alkyl ester monomer having 19 to 30 carbon atoms in R 2 in the above formula (1) (hereinafter also referred to as "monomer (a2)") are particularly preferably used in combination.

[0061] The monomer (a1) may also be R in the above formula (1) 2A 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 (1). 2 A mixture of two or more of the (meth)acrylic long-chain alkyl ester monomers having 19 to 30 carbon atoms.

[0062] 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 water repellency is excellent. When the carbon number is at most the aforementioned upper limit value, the availability and processability are excellent.

[0063] 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 water repellency is excellent. When the carbon number is at most the aforementioned upper limit value, the availability and processability are excellent.

[0064] 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 45% by mass, more preferably 5 to 40% by mass, still more 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 water repellency after washing is better.

[0065] When the monomers (a1) and (a2) are used in combination, the proportion of the structural unit based on the monomer (a2) is preferably 55 to 99% by mass, more preferably 60 to 95% by mass, still more 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 water repellency after washing is better.

[0066] 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, particularly preferably 85% by mass or more, and may also be 100% 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 good. When the aforementioned proportion is at most the aforementioned upper limit value, the water repellency after washing is better.

[0067] (Monomer (b))

[0068] The monomer (b) is a vinyl halide. As the monomer (b), a vinyl halide having one or two halogen atoms is preferred, and a vinylidene dihalide having two halogen atoms is more preferred.

[0069] The halogen atom of the aforementioned 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. Additionally, when the aforementioned vinyl halide has two or more halogen atoms, the multiple halogen atoms may be the same or different at will.

[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 monomer having two or more (meth)acryloyl groups. As monomer (c), a monomer having two or more (meth)acryloyl groups represented by the following formula (2) is preferred.

[0074] Q-(R 4 C(=O)CR 3 =CH2) n (2)

[0075]

[0076] In the aforementioned formula (2), n represents an integer of 2 to 10, R 3 represents H, CH3, or a chlorine atom, R 4 represents a single bond or a divalent organic group, Q represents a linear or branched alkylene group having 1 to 16 carbon atoms, a residue obtained by removing hydrogen from the hydroxyl group of a polyhydric alcohol, a trivalent group represented by the aforementioned formula (3), or a trivalent group represented by the aforementioned formula (4), and multiple (R 4 C(=O)CR 3 =CH2) may be the same or different at will. In the aforementioned formula (3) and the aforementioned formula (4), * represents a bonding site. Among them, when Q is a linear or branched alkylene group having 1 to 16 carbon atoms or a residue obtained by removing hydrogen from the hydroxyl group of a polyhydric alcohol, the atom in R 4 bonded to Q is an atom other than an oxygen atom.

[0077] n is an integer of 2 to 10, preferably an integer of 2 to 8, and more preferably an integer of 2 to 6.

[0078] R 3 represents H, CH3, or a chlorine atom. R 3 is preferably H or CH3.

[0079] R 4 represents a single bond or a divalent organic group. When R 4 is a divalent organic group, the carbon number of R 4 is preferably 2 to 12, more preferably 2 to 8, and still more preferably 1 to 6.

[0080] When Q is a linear or branched alkylene group having 1 to 16 carbon atoms or a residue obtained by removing hydrogen from the hydroxyl group of a polyol, R 4 preferably does not have an oxygen atom.

[0081] R 4 is a single bond or an alkylene group, Q is a linear or branched alkylene group having 1 to 16 carbon atoms, and when the total number of carbon atoms of Q and R 4 is 16 or less, Q is a linear or branched alkylene group having 1 to 16 carbon atoms, and R 4 is a single bond.

[0082] When Q is a residue obtained by removing hydrogen from the hydroxyl group of a polyol or a trivalent group represented by the aforementioned formula (4), R 4 is preferably a single bond. When Q is a linear or branched alkylene group having 1 to 16 carbon atoms or a trivalent group represented by the aforementioned formula (3), R 4 is preferably a divalent organic group.

[0083] R 4 When it is a divalent organic group, R 4 is preferably a divalent hydrocarbon group and a divalent organic group in which one or more carbon atoms in the divalent hydrocarbon group are replaced by a heteroatom, or an organic group containing no carbon atoms.

[0084] Examples of the divalent hydrocarbon group include a divalent saturated hydrocarbon group and a divalent unsaturated hydrocarbon group. 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 triple bond.

[0085] Examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom, preferably a nitrogen atom and an oxygen atom. When R 4 contains a heteroatom, the number of heteroatoms is preferably 1 to 4, more preferably 1 to 3.

[0086] R 4 is linear or branched, preferably linear.

[0087] R 4 When it is a divalent organic group, R 4 is preferably a divalent group represented by the following formula (5) or (6).

[0088] -R 5 -NH-R 6 -Formula (5)

[0089] -R 7 -O-R 8 Formula (6)

[0090] In the aforementioned formulas (5) and (6), R 5 to R 8Each is independently a single bond or an alkylene group having 1 to 6 carbon atoms. R 5 is bonded to Q, and R 6 is bonded to C(=O). R 7 is bonded to Q, and R 8 is bonded to C(=O). The alkylene group may be straight-chain or branched-chain, preferably straight-chain.

[0091] The number of carbon atoms of the alkylene group is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2.

[0092] In the aforementioned formula (5), preferably R 5 and R 6 are divalent groups that are single bonds.

[0093] In the aforementioned formula (6), preferably R 7 is an alkylene group having 1 to 6 carbon atoms, and R 8 is a divalent group that is a single bond.

[0094] When Q is a straight-chain or branched-chain alkylene group having 1 to 16 carbon atoms, the number of carbon atoms of Q is preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 3. The alkylene group is preferably straight-chain.

[0095] Examples of the alkylene group include methylene, ethylene, propylene, isopropylidene, butylene, and the like.

[0096] When Q is a residue obtained by removing hydrogen from the hydroxyl group of a polyol, the number of hydroxyl groups of the aforementioned polyol is preferably 2 to 10, more preferably 2 to 8, and still more preferably 2 to 6. The aforementioned polyol may be straight-chain or branched-chain.

[0097] The number of carbon atoms of the aforementioned polyol is preferably 2 to 20, more preferably 2 to 18, and still more preferably 3 to 15.

[0098] Examples of the polyol include compounds in which 2 to 10 hydrogen atoms in a hydrocarbon compound optionally having an etheric oxygen atom are replaced by hydroxyl groups. The aforementioned hydrocarbon compound may be a saturated hydrocarbon compound or an unsaturated hydrocarbon compound. Examples of the unsaturated hydrocarbon compound include compounds in which one or more carbon-carbon single bonds in the aforementioned saturated hydrocarbon compound are replaced by a carbon-carbon double bond or triple bond, and compounds having an aromatic ring. The aromatic ring may be included in the form of an aryl group or in the form of an arylene group. When the polyol is a compound having an aromatic ring, the number of aromatic rings is preferably 1 or 2.

[0099] When the polyol has an etheric oxygen atom, the number of etheric oxygen atoms is preferably 1 to 5, more preferably 1 to 4, and still more preferably 1 to 3.

[0100] As the monomer (c), for example, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,10-decanediol diacrylate, 1,10-decanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, di(trimethylolpropane) tetraacrylate, di(trimethylolpropane) tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, tris(2-acryloyloxyethyl) isocyanurate, tris(2-methacryloyloxyethyl) isocyanurate, 1,3,5-triacryloylhexahydro-1,3,5-triazine, 1,3,5-trimethacryloylhexahydro-1,3,5-triazine, N,N'-methylenebisacrylamide, N,N'-methylenebis-methacrylamide can be cited.

[0101] Two or more kinds of the monomer (c) can be used in combination.

[0102] (Monomer (d))

[0103] The monomer (d) is a monomer having a crosslinkable functional group and one group polymerizable with a (meth)acryloyl group or a monomer having two or more groups polymerizable with a (meth)acryloyl group (wherein, a monomer having two or more (meth)acryloyl groups is not included).

[0104] By making the polymer (A) have a structural unit based on the monomer (d), the washing and rubbing durability is further improved.

[0105] As the group polymerizable with a (meth)acryloyl group, a group having a carbon-carbon double bond at the molecular terminal can be exemplified. For example, a (meth)acryloyl group, a vinyl group, and an allyl group are preferable.

[0106] As the crosslinkable functional group, 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 by the interaction of the foregoing bonds is preferable.

[0107] As the foregoing functional group, an isocyanate group, a blocked isocyanate group, an alkoxysilyl group, a primary amino group, an alkoxymethylamide group, a silanol group, a primary amide group, an epoxy group, a hydroxyl group, an oxazoline group, a carboxyl group, a sulfonic acid group, etc. are preferable, and a hydroxyl group, a blocked isocyanate group, a primary amino group, or an epoxy group is particularly preferable.

[0108] As the monomer (d), (meth)acrylate esters, (meth)acrylamides, vinyl ethers having a crosslinkable functional group, or vinyl esters having a crosslinkable functional group are preferable.

[0109] As the monomer (d), the following compounds can be cited.

[0110] 2-Isocyanatoethyl (meth)acrylate, 3-Isocyanatopropyl (meth)acrylate, 4-Isocyanatobutyl (meth)acrylate, 2-Butanone oxime adduct of 2-isocyanatoethyl (meth)acrylate, Pyrazole adduct of 2-isocyanatoethyl (meth)acrylate, 3,5-Dimethylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate, 3-Methylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate, ε-Caprolactam adduct of 2-isocyanatoethyl (meth)acrylate, 2-Butanone oxime adduct of 3-isocyanatopropyl (meth)acrylate, Pyrazole adduct of 3-isocyanatopropyl (meth)acrylate.

[0111] 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.

[0112] Methoxymethyl (meth)acrylamide, Ethoxymethyl (meth)acrylamide, Butoxymethyl (meth)acrylamide, Diacetone acrylamide, γ-Methacryloyloxypropyltrimethoxysilane, Trimethoxyvinylsilane, Vinyltrimethoxysilane.

[0113] Tert-butyl (meth)acrylamidosulfonic acid, (meth)acrylamide, N-Hydroxymethyl (meth)acrylamide, N-Butoxymethyl (meth)acrylamide, Diacetone (meth)acrylamide, (meth)acrylic acid glycidyl ester, 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-(Methacryloyloxy)ethyl succinate, 2-(Methacryloyloxy)hexahydrophthalate, 2-(Methacryloyloxy)ethyl acid phosphate, Allyl (meth)acrylate, 2-Vinyl-2-oxazoline, Polycaprolactone of hydroxyethyl (meth)acrylate of 2-vinyl-4-methyl-(2-vinyloxazoline).

[0114] Tris(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 Kyoto Silk Kayaku Co., Ltd.). Polycaprolactone of hydroxyethyl (meth)acrylate (Placcel FA, FM series, manufactured by Daicel Chemical Industries, Ltd.).

[0115] As monomer (d), N-hydroxymethyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, 3-chloro-2-hydroxypropyl methacrylate, or polycaprolactone of hydroxyethyl (meth)acrylate (Placcel FA, FM series, manufactured by Daicel Chemical Industries, Ltd.), 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate is preferred.

[0116] Two or more kinds of monomer (d) can be used in combination.

[0117] (Monomer (e))

[0118] Monomer (e) is a monomer other than monomer (a), monomer (b), monomer (c), and monomer (d).

[0119] As monomer (e), the following compounds can be cited.

[0120] (Methyl) acrylate, (ethyl) acrylate, (propyl) acrylate, (butyl) acrylate, (cyclohexyl) acrylate, (2-ethylhexyl) acrylate, (n-hexyl) acrylate, (benzyl) acrylate, (octyl) acrylate, (decyl) methacrylate, (cyclododecyl) acrylate, (3-ethoxypropyl) acrylate, (methoxybutyl) acrylate, (2-ethylbutyl) acrylate, (1,3-dimethylbutyl) acrylate, (2-methylpentyl) acrylate.

[0121] 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, cyclopentanoyloxyethylene, cyclopentylacetoxyethylene, styrene, α-methylstyrene, p-methylstyrene, hexylstyrene, octylstyrene, nonylstyrene.

[0122] N-methyl(meth)acrylamide, 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, (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxypropyltrimethylammonium chloride, (meth)acrylamideethyltrimethylammonium chloride, (meth)acrylamidepropyltrimethylammonium chloride, (meth)acryloylmorpholine.

[0123] Vinyl alkyl ether, haloalkyl vinyl ether, vinyl alkyl ketone, aziridinylethyl (meth)acrylate, 2-ethylhexyl polyoxyalkylene (meth)acrylate, polyoxyalkylene di(meth)acrylate.

[0124] Alkyl crotonate, alkyl maleate, alkyl fumarate, alkyl citraconate, alkyl mesaconate, triallyl cyanurate, allyl acetate, N-vinylcarbazole, maleimide, N-methylmaleimide, (meth)acrylate having silicone in the side chain, (meth)acrylate having urethane, (meth)acrylate having a polyoxyalkylene chain with an alkyl group having 1 to 4 carbon atoms at the end, alkylene di(meth)acrylate.

[0125] Two or more kinds of the monomer (e) can be used in combination.

[0126] With respect to all the units constituting the polymer (A), the total proportion of the units (a), (b) and (c) is preferably 70% by mass or more, more preferably 75 to 98% by mass, and still more preferably 80 to 97% by mass. When the total proportion of the units (a), (b) and (c) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent.

[0127] When the polymer (A) contains either or both of the units (d) and (e), with respect to all the units constituting the polymer (A), the total proportion of the units (a), (b) and (c) is preferably 75 to 98% by mass, more preferably 80 to 97% by mass.

[0128] The proportion of unit (a) is preferably 50 to 90% by mass, more preferably 55 to 90% by mass, and still more preferably 60 to 85% by mass, relative to all the units constituting polymer (A). When the proportion of unit (a) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the proportion of unit (a) is at most the above upper limit value, units (b), (c) and other units can be sufficiently contained, and the water repellency of the article treated with this composition is more excellent.

[0129] The proportion of unit (b) is preferably 5 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 8 to 20% by mass, relative to all the units constituting polymer (A). When the proportion of unit (b) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the proportion of unit (b) is at most the above upper limit value, units (a), (c) and other units can be sufficiently contained, and the water repellency of the article treated with this composition is more excellent.

[0130] The proportion of unit (c) is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and still more preferably 1 to 10% by mass, relative to all the units constituting polymer (A). When the proportion of unit (c) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the proportion of unit (c) is at most the above upper limit value, units (a), (b) and other units can be sufficiently contained, and the water repellency of the article treated with this composition is more excellent.

[0131] The total proportion of unit (a) and unit (b) is preferably at least 55% by mass, more preferably 60 to 98% by mass, and still more preferably 68 to 96% by mass, relative to all the units constituting polymer (A). When the total proportion of unit (a) and unit (b) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the proportion of unit (a) and unit (b) is at most the above upper limit value, unit (c) and other units can be sufficiently contained, and the water repellency of the article treated with this composition is more excellent.

[0132] The total proportion of unit (b) and unit (c) is preferably 5.1 to 50% by mass, more preferably 5.5 to 40% by mass, and still more preferably 6 to 30% by mass, relative to all the units constituting polymer (A). When the total proportion of unit (b) and unit (c) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the proportion of unit (b) and unit (c) is at most the above upper limit value, unit (a) and other units can be sufficiently contained, and the water repellency of the article treated with this composition is more excellent.

[0133] The total proportion of unit (c) and unit (a) is preferably 50.1 to 95% by mass, more preferably 55 to 90% by mass, and still more preferably 60 to 90% by mass, relative to all the units constituting polymer (A). When the total proportion of unit (c) and unit (a) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the proportion of unit (c) and unit (a) is at most the above upper limit value, unit (b) and other units can be sufficiently contained, and the water repellency of the article treated with this composition is more excellent.

[0134] The mass ratio of unit (a) / unit (b) is preferably 1.6 to 19, more preferably 2.2 to 18, and still more preferably 3 to 10. When the mass ratio of unit (a) / unit (b) is at least the above lower limit value, the water repellency 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).

[0135] The mass ratio of unit (b) / unit (c) is preferably 0.25 to 300, more preferably 0.3 to 50, and still more preferably 0.8 to 20. When the mass ratio of unit (b) / unit (c) is at least the above lower limit value, the water repellency 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).

[0136] The mass ratio of unit (c) / unit (a) is preferably 0.001 to 0.4, more preferably 0.005 to 0.27, and still more preferably 0.010 to 0.17. When the mass ratio of unit (c) / unit (a) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the mass ratio of unit (c) / unit (a) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0137] The mass ratio of {unit (a) + unit (b)} / unit (c) is preferably 2.75 to 950, more preferably 4 to 800, and still more preferably 6 to 200. When the mass ratio of {unit (a) + unit (b)} / unit (c) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the mass ratio of {unit (a) + 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).

[0138] When the polymer (A) contains the unit (d), the proportion of the unit (d) is preferably 0.1 to 15% by mass, more preferably 0.2 to 10% by mass, and still more preferably 0.5 to 6% by mass, relative to all the units constituting the polymer (A). When the proportion of the unit (d) is at least the above lower limit value, the water repellency of the article treated with the present composition is more excellent. When the proportion of the unit (d) is at most the above upper limit value, the units (a), (b), (c) and other units can be sufficiently contained, and the water repellency of the article treated with the present composition is more excellent.

[0139] When the polymer (A) contains the unit (e), the proportion of the unit (e) is preferably 0.1 to 15% by mass, more preferably 0.2 to 10% by mass, and still more preferably 0.5 to 6% by mass, relative to all the units constituting the polymer (A). When the proportion of the unit (e) is at least the above lower limit value, the water repellency of the article treated with the present composition is more excellent. When the proportion of the unit (e) is at most the above upper limit value, the units (a), (b), (c) and other units can be sufficiently contained, and the water repellency of the article treated with the present composition is more excellent.

[0140] When the polymer (A) contains the unit (d) or the unit (e), the total proportion of the unit (d) and the unit (e) is preferably 0.2 to 30% by mass, more preferably 0.4 to 20% by mass, and still more preferably 1 to 12% by mass, relative to all the units constituting the polymer (A). When the proportion of the unit (d) and the unit (e) is at least the above lower limit value, the water repellency of the article treated with the present composition is more excellent. When the proportion of the unit (d) and the unit (e) is at most the above upper limit value, the units (a), (b), (c) can be sufficiently contained, and the water repellency of the article treated with the present composition is more excellent.

[0141] The proportion of each unit can be calculated by the reaction rate of each monomer component obtained by 1 1H-NMR, gas chromatography, and high performance liquid chromatography. When the conversion rate of the monomer component into 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.

[0142] The Mn of the polymer (A) is preferably 5,000 to 100,000, more preferably 8,000 to 90,000, and still more preferably 10,000 to 60,000. When the Mn of the polymer (A) is at least the above lower limit value, the water repellency of the article treated with the present 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.

[0143] The Mw of polymer (A) is preferably from 8,000 to 1,000,000, more preferably from 12,000 to 900,000, and still more preferably from 15,000 to 800,000. When the Mw of polymer (A) is at or above the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the Mw of polymer (A) is at or below the above upper limit value, the water dispersibility of polymer (A) is more excellent.

[0144] (medium)

[0145] 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.

[0146] Examples of the alcohol include 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.

[0147] Examples of the glycol or glycol ether include 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.

[0148] Examples of the halogen compound include halogenated hydrocarbon, halogenated ether, etc. The halogen compound preferably does not contain fluorine. Examples of the halogenated hydrocarbon include hydrochlorofluorocarbon, hydrobromofluorocarbon, etc.

[0149] Examples of the hydrocarbon include aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, etc.

[0150] As aliphatic hydrocarbons, 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.

[0151] As alicyclic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. can be cited.

[0152] As aromatic hydrocarbons, benzene, toluene, xylene, etc. can be cited.

[0153] As ketones, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, etc. can be cited.

[0154] As esters, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, methyl lactate, ethyl lactate, pentyl lactate, etc. can be cited.

[0155] As ethers, diisopropyl ether, dioxane, tetrahydrofuran, etc. can be cited.

[0156] As nitrogen compounds, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can be cited.

[0157] As sulfur compounds, dimethyl sulfoxide, sulfolane, etc. can be cited.

[0158] As inorganic solvents, liquid carbon dioxide can be cited.

[0159] As organic acids, acetic acid, propionic acid, malic acid, lactic acid, etc. can be cited.

[0160] The medium can be used alone as one kind, or two or more kinds can be used in combination. When two or more kinds of media are used in combination, it is preferably used in combination with water. By using a 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.

[0161] 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 with respect to 100 parts by mass of water.

[0162] (Surfactant)

[0163] As surfactants, hydrocarbon-based surfactants can be cited. As hydrocarbon-based surfactants, anionic surfactants, nonionic surfactants, cationic surfactants, or amphoteric surfactants can be cited.

[0164] As a surfactant, from the aspect of dispersion stability, a combination of a nonionic surfactant and a cationic surfactant or an amphoteric surfactant is preferably used, or a single anionic surfactant is preferably used, and a combination of a nonionic surfactant and a cationic surfactant is preferably used.

[0165] The mass ratio of the nonionic surfactant to the cationic surfactant is preferably 97 / 3 to 40 / 60.

[0166] 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 made small, and thus the adverse effect on the water repellency of the article can be reduced.

[0167] As the nonionic surfactant, one or more selected from the group consisting of surfactants s 1 ~s 6 are preferably used.

[0168] Surfactant s 1 :

[0169] Surfactant s 1 is a polyoxyalkylene monoalkyl ether, a polyoxyalkylene monoalkenyl ether, or a polyoxyalkylene monoalkapolyenyl ether.

[0170] As surfactant s 1 , polyoxyalkylene monoalkyl ether or polyoxyalkylene monoalkenyl ether is preferred. Surfactant s 1 can be used alone, or two or more thereof can be used in combination.

[0171] As the alkyl, alkenyl, or alkapolyenyl group (hereinafter, the alkyl, alkenyl, and alkapolyenyl groups are collectively referred to as R s group), a group having 4 to 26 carbon atoms is preferred. R s group can be linear or branched. As the branched R s group, a secondary alkyl group, a secondary alkenyl group, or a secondary alkapolyenyl group is preferred.

[0172] As specific examples of the R s group, octyl, dodecyl, tetradecyl, hexadecyl, stearyl (octadecyl), behenyl (docosyl), oleyl (9-octadecenyl), etc. can be mentioned.

[0173] As the polyoxyalkylene (hereinafter referred to as POA) chain, preferably a chain formed by connecting any one or both of a polyoxyethylene (hereinafter referred to as POE) chain and a polyoxypropylene (hereinafter referred to as POP) chain two or more times. The POA chain may be a chain containing one type of POA chain or a chain containing two or more types of POA chains. In the case of containing two or more types of POA chains, each POA chain is preferably connected in a block form.

[0174] As the surfactant s 1 , more preferably the compound (s 11 ).

[0175] R 10 O[CH2CH(CH3)O] s -(CH2CH2O) r H···(s 11 ).

[0176] 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.

[0177] When r is 5 or more, it is soluble in water and uniformly dissolved in an 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.

[0178] When s is 20 or less, it is soluble in water and uniformly dissolved in an aqueous medium, so the water repellent composition has good permeability to the article.

[0179] When r and s are 2 or more, the POE chain and the POP chain are connected in a block form.

[0180] As R 10 , preferably straight-chain or branched-chain.

[0181] r is preferably an integer of 10 to 30.

[0182] s is preferably an integer of 0 to 10.

[0183] 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.

[0184] C 18 H 37 O[CH2CH(CH3)O]2-(CH2CH2O) 30 H,

[0185] C 18 H 35 O-(CH2CH2O) 30 H,

[0186] C 16 H 33 O[CH2CH(CH3)O]5-(CH2CH2O) 20 H、

[0187] C 12 H 25 O[CH2CH(CH3)O]2-(CH2CH2O) 15 H、

[0188] (C8H 17 )(C6H 13 )CHO-(CH2CH2O) 15 H、

[0189] C 10 H 21 O[CH2CH(CH3)O]2-(CH2CH2O) 15 H、

[0190] Surfactant s 2 :

[0191] Surfactant s 2 is a compound having more than 1 carbon-carbon triple bond and more than 1 hydroxyl group in the molecule.

[0192] As surfactant s 2 , preferably a compound having 1 carbon-carbon triple bond and 1 or 2 hydroxyl groups in the molecule.

[0193] Surfactant s 2 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 randomly connected, or a chain in which a POE chain and a POP chain are block-connected can be cited.

[0194] As surfactant s 2 , preferably compound (s 21 ) to (s 24 ).

[0195] HO-C(R 11 )(R 12 )-C≡C-C(R 13 )(R 14 )-OH ··· (s 21 ),

[0196] HO-(A 1 O) u -C(R 11 )(R 12 )-C≡C-C(R13 )(R 14 )-(OA 2 ) v -OH···(s 22 )、HO-C(R 15 )(R 16 )-C≡C-H···(s 23 )、

[0197] HO-(A 3 O) w -C(R 15 )(R 16 )-C≡C-H···(s 24 )。

[0198] A 1 ~A 3 Each is an alkylene group.

[0199] u and v are each an integer of 0 or more, and (u + v) is an integer of 1 or more.

[0200] w is an integer of 1 or more.

[0201] When u, v, and w are each 2 or more, A 1 ~A 3 may be the same or different from each other.

[0202] 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.

[0203] R 11 ~R 16 Each is a hydrogen atom or an alkyl group.

[0204] 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.

[0205] As the compound(s 22 )), the compound(s 25 ) is preferred.

[0206]

[0207] Among them, x and y are each an integer of 0 to 100.

[0208] The compound(s 25 ) can be used alone or in combination of two or more.

[0209] As the compound(s 25), preferably a compound where x and y are 0, a compound where the average of the sum of x and y is 1 to 4, or a compound where the average of the sum of x and y is 10 to 30.

[0210] Surfactant s 3 :

[0211] 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.

[0212] As the aforementioned POA chain, either or both of polyoxytetramethylene (hereinafter referred to as POT.) and POP chain are preferred.

[0213] As surfactant s 3 , preferably compound (s 31 ) or compound (s 32 ).

[0214] HO(CH2CH2O) g1 (C3H6O) t (CH2CH2O) g2 H···(s 31 )、

[0215] HO(CH2CH2O) g1 (CH2CH2CH2CH2O) t (CH2CH2O) g2 H···(s 32 ).

[0216] g1 is an integer from 0 to 200.

[0217] t is an integer from 2 to 100.

[0218] g2 is an integer from 0 to 200.

[0219] When g1 is 0, g2 is an integer of 2 or more. When g2 is 0, g1 is an integer of 2 or more.

[0220] -C3H6- can be -CH(CH3)CH2-, can be -CH2CH(CH3)-, or can be a mixture of -CH(CH3)CH2- and -CH2CH(CH3)-.

[0221] The POA chain is block-shaped.

[0222] As surfactant s 3 , the following compounds can be cited.

[0223] HO-(CH2CH2O) 15-(C3H6O) 35 -(CH2CH2O) 15 H、

[0224] HO-(CH2CH2O)8-(C3H6O) 35 -(CH2CH2O)8H、

[0225] HO-(CH2CH2O) 45 -(C3H6O) 17 -(CH2CH2O) 45 H、

[0226] HO-(CH2CH2O) 34 -(CH2CH2CH2CH2O) 28 -(CH2CH2O) 34 H。

[0227] Surfactant s 4 :

[0228] Surfactant s 4 is a compound having an amine oxide moiety in the molecule.

[0229] As surfactant s 4 , preferably compound(s 41 ).

[0230] (R 17 )(R 18 )(R 19 )N(→O)···(s 41 ).

[0231] R 17 ~R 19 are each a monovalent hydrocarbon group.

[0232] In this specification, a surfactant having an amine oxide (N→O) is regarded as a nonionic surfactant.

[0233] Compound(s 41 ) can be used singly or in combination of two or more.

[0234] As compound(s 41 ), from the aspect of the dispersion stability of the polymer, preferably compound(s 42 ).

[0235] (R 20 )(CH3)2N(→O)···(s 42 ).

[0236] R 20is 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.

[0237] As the compound (s 42 ), the following compounds can be cited.

[0238] [H(CH2) 12 (CH3)2N(→O),

[0239] [H(CH2) 14 (CH3)2N(→O),

[0240] [H(CH2) 16 (CH3)2N(→O),

[0241] [H(CH2) 18 (CH3)2N(→O).

[0242] Surfactant s 5 :

[0243] Surfactant s 5 is a condensate of polyoxyethylene mono (substituted phenyl) ether or polyoxyethylene mono (substituted phenyl) ether.

[0244] As the substituted phenyl, a phenyl substituted with a monovalent hydrocarbon group is preferred, and a phenyl substituted with an alkyl group, an alkenyl group or a styryl group is more preferred.

[0245] As surfactant s 5 , a condensate of polyoxyethylene mono (alkylphenyl) ether, a condensate of polyoxyethylene mono (alkenylphenyl) ether, polyoxyethylene mono (alkylphenyl) ether, polyoxyethylene mono (alkenylphenyl) ether, or polyoxyethylene mono [(alkyl) (styryl) phenyl] ether is preferred.

[0246] As the condensate of polyoxyethylene mono (substituted phenyl) ether or polyoxyethylene mono (substituted phenyl) ether, a formaldehyde condensate 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.

[0247] Surfactant s 6 :

[0248] Surfactant s 6 is a fatty acid ester of a polyol.

[0249] The polyol represents glycerin, sorbitan, sorbitol, polyglycerol, polyethylene glycol, polyoxyethylene glycerol ether, polyoxyethylene sorbitan ether, or polyoxyethylene sorbitol ether.

[0250] As the surfactant s 6 , examples include the 1:1 (molar ratio) ester of stearic acid and polyethylene glycol, the 1:4 (molar ratio) ester of the ether of sorbitol and polyethylene glycol with oleic acid, the 1:1 (molar ratio) ester of the ether of polyoxyethylene and sorbitan with stearic acid, the 1:1 (molar ratio) ester of the ether of polyethylene glycol and sorbitan with oleic acid, the 1:1 (molar ratio) ester of dodecanoic acid and sorbitan, the 1:1 or 2:1 (molar ratio) ester of oleic acid and decaglycerol, and the 1:1 or 2:1 (molar ratio) ester of stearic acid and decaglycerol.

[0251] The surfactant s 7 :

[0252] When the surfactant contains a cationic surfactant, as the aforementioned cationic surfactant, the surfactant s 7 is preferred.

[0253] The surfactant s 7 is a substituted ammonium salt.

[0254] As the surfactant s 7 , an ammonium salt in which one or more of the hydrogen atoms bonded to the nitrogen atom are substituted by an alkyl group, an alkenyl group, or a POA chain terminated with a hydroxyl group is preferred, and the compound (s 71 ) is more preferred.

[0255] [(R 21 )4N + ·X - ···(s 71 ).

[0256] 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 terminated with a hydroxyl group. The four Rs 21 are optionally the same or different, provided that the four Rs 21 are not simultaneously hydrogen atoms.

[0257] As R 21 , a long-chain alkyl group having 6 to 22 carbon atoms or a long-chain alkenyl group having 6 to 22 carbon atoms is preferred.

[0258] R 21 When R 21 is an alkyl group other than a long-chain alkyl group, as R

[0259] R 21In the case of a POA chain having a hydroxyl group at the end, as the POA chain, a POE chain is preferred.

[0260] X - is a counter ion.

[0261] As X - , chloride ion, ethyl sulfate ion, or acetate ion is preferred.

[0262] As the compound(s 71 ), 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. can be mentioned.

[0263] Surfactant s 8 :

[0264] When the surfactant contains an amphoteric surfactant, as the aforementioned amphoteric surfactant, surfactant s 8 is preferred.

[0265] Surfactant s 8 is alanine type, imidazolium betaine type, amide betaine type or acetate betaine.

[0266] As the hydrophobic group possessed by surfactant s 8 , a long-chain alkyl group having 6 to 22 carbon atoms or a long-chain alkenyl group having 6 to 22 carbon atoms is preferred.

[0267] As surfactant s 8 , lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolium betaine, lauryl dimethylaminoacetic acid betaine, fatty acid amide propyl dimethylaminoacetic acid betaine, etc. can be mentioned.

[0268] Surfactant s 9 :

[0269] As the surfactant, surfactant s 9 can be used.

[0270] Surfactant s 9 is a block copolymer, random copolymer, or a hydrophobic modified product of a hydrophilic copolymer composed of a hydrophilic monomer and a hydrocarbon-based hydrophobic monomer.

[0271] 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, methylcellulose, hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, etc.

[0272] As surfactant s 9 Commercially available products thereof include MP polymers (product numbers: MP-103, MP-203) from Kuraray Co., Ltd., SMA resins from Elf Atochem, METOLOSE from Shin-Etsu Chemical Co., Ltd., EPOMIN RP from Nippon Shokubai Co., Ltd., etc.

[0273] 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 s 7 combination, and more preferably surfactant s 7 is the above combination of compound (s 71 ). The total amount of the surfactants is preferably 1 to 10 parts by mass, more preferably 1 to 7 parts by mass, relative to the polymer (100 parts by mass).

[0274] (Molecular weight regulator)

[0275] 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.) are exemplified, and n-dodecyl mercaptan, tert-dodecyl mercaptan, and stearyl mercaptan are particularly preferred.

[0276] (Polymerization initiator)

[0277] As a polymerization initiator, for example, a thermal polymerization initiator, a photopolymerization initiator, a radiation polymerization initiator, a radical polymerization initiator, or an ionic polymerization initiator can be cited, and a radical polymerization initiator is preferred. As the radical polymerization initiator, for example, an azo-based polymerization initiator, a peroxide-based polymerization initiator, or a redox initiator can be used according to the polymerization temperature. As the radical polymerization initiator, an azo-based compound is preferred, and a salt of an azo-based compound is more preferred. As the initiator, for example, the 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 cited. The polymerization temperature is preferably 30 to 80°C.

[0278] (Other components)

[0279] The water repellent composition of the present embodiment may further contain other components as needed.

[0280] As the other components, a crosslinking agent, a penetrant, an antifoaming agent, a water absorbent, an antistatic agent, an antistatic polymer, an anti-wrinkle agent, a hand modifier, a film-forming aid, a water-soluble polymer (such as polyacrylamide, polyvinyl alcohol, etc.), a thermosetting agent (such as melamine resin, urethane resin, a compound containing a triazine ring, an isocyanate-based compound, etc.), an epoxy curing agent (such as isophthalic dihydrazide, adipic dihydrazide, sebacic dihydrazide, dodecanedioic dihydrazide, 1,6-hexamethylenebis(N,N-dimethylaminourea), 1,1,1',1'-tetramethyl-4,4'-(methylenedi-p-phenylene)diaminourea, spirodiol, etc.), a thermosetting catalyst, a crosslinking catalyst, a synthetic resin, a fiber stabilizer, an inorganic fine particle, etc. can be cited.

[0281] The water repellent composition of the present embodiment may contain, as needed, a polymer capable of exhibiting water repellency other than the polymer (A) of the present embodiment, a commercially available water repellent, a water repellent compound not having a fluorine atom, etc. As the water repellent compound not having a fluorine atom, a paraffin-based compound, an aliphatic amide-based compound, an alkylethyleneurea compound, a silicon-based compound, etc. can be cited.

[0282] When the composition contains a crosslinking agent, the adhesion to the substrate is likely to be improved.

[0283] As the crosslinking agent, an isocyanate-based crosslinking agent, a hydroxymethyl-based crosslinking agent, a carbodiimide-based crosslinking agent, and an oxazoline-based crosslinking agent are preferred.

[0284] As the isocyanate-based crosslinking agent, an isocyanate-based crosslinking agent having two or more isocyanate groups is preferred.

[0285] As the isocyanate-based crosslinking agent, for example, an aromatic-blocked isocyanate-based crosslinking agent, an aliphatic-blocked isocyanate-based crosslinking agent, an aromatic non-blocked isocyanate-based crosslinking agent, and an aliphatic non-blocked isocyanate-based crosslinking agent can be cited. The isocyanate-based crosslinking agent is preferably a water-dispersion type emulsified with a surfactant or a self-water-dispersion type having a hydrophilic group.

[0286] 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.

[0287] 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 and the like.

[0288] The oxazoline-based crosslinking agent is a polymer having an oxazoline group in the molecule and is a crosslinking agent that shows excellent reactivity with carboxyl groups of articles and the like.

[0289] As other crosslinking agents, for example, divinyl sulfone, polyamides and their cationic derivatives, polyamines and their 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 salts of chloromethyl ether of ethylene glycol, polyamine-polyamide-epichlorohydrin resin, polyvinyl alcohol or its derivatives, polyacrylamide or its derivatives, and glyoxal resin-based anti-crease agents can be cited.

[0290] When this composition contains a hydroxymethyl-based crosslinking agent or a glyoxal resin-based anti-crease 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.

[0291] (Ratio of each component)

[0292] 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.

[0293] 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.

[0294] Regarding the solid component concentration of the present composition, when the present 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.

[0295] It should be noted that the solid component concentration is the total content of the polymer (A) and the surfactant in the present composition.

[0296] The proportion of the polymer (A) relative to the total mass of the present 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.

[0297] When the present composition contains a surfactant, the content of the surfactant in the present 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 relative to 100 parts by mass of the polymer (A).

[0298] When the present composition contains a molecular weight regulator, the content of the molecular weight regulator in the present composition is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, further preferably 0.5 to 9 parts by mass, and even further preferably 1 to 8 parts by mass relative to 100 parts by mass of the polymer (A).

[0299] When the present composition contains a polymerization initiator, the content of the polymerization initiator in the present composition is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and further preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the polymer (A).

[0300] Relative to the total mass of the present composition, the content of fluorine atoms is preferably 0.1% by mass or less, more preferably 0% by mass. The content of fluorine atoms relative to the total mass of the present composition can be measured by combustion ion chromatography or the like.

[0301] Method for Manufacturing Non-Fluorine Polymer

[0302] The method for manufacturing the non-fluorine polymer of the present embodiment is the following manufacturing method: polymerize a mixture containing monomer components in the presence of a surfactant and a polymerization initiator, and the monomer components include monomer (a), monomer (b), and monomer (c). In addition, a water repellent composition is also manufactured.

[0303] The monomer components may further include either or both of monomer (d) and monomer (e).

[0304] For each of monomer (a), monomer (b), monomer (c), monomer (d), and monomer (e), a substance manufactured by a known manufacturing method can be used. Regarding commercially available monomers, commercially available products can be used.

[0305] The total proportion of monomer (a), monomer (b), and monomer (c) contained in the mixture is preferably 70% by mass or more, more preferably 75 to 98% by mass, and still more preferably 80 to 97% by mass, relative to the total mass of the monomers constituting the non-fluorine polymer. When the total proportion of monomer (a), monomer (b), and monomer (c) is at least the above lower limit value, the water repellency and washing durability of the article treated with this composition are excellent.

[0306] When the monomer component contains either or both of monomer (d) and monomer (e), the total proportion of monomer (a), monomer (b), and monomer (c) contained in the mixture is preferably 75 to 98% by mass, more preferably 80 to 97% by mass, relative to the total mass of the monomers constituting the non-fluorine polymer.

[0307] The proportion of monomer (a) contained in the mixture is preferably 50 to 90% by mass, more preferably 55 to 90% by mass, and still more preferably 60 to 85% by mass, relative to the total mass of the monomers constituting the non-fluorine polymer. When the proportion of monomer (a) is at least the above lower limit value, the water repellency 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) and monomer (c) can be sufficiently contained, and the water repellency of the article treated with this composition is more excellent.

[0308] The proportion of monomer (b) contained in the mixture is preferably 5 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 8 to 20% by mass, relative to the total mass of the monomers constituting the non-fluorine polymer. When the proportion of monomer (b) is at least the above lower limit value, the water repellency 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 (c) and monomer (a) can be sufficiently contained, and the water repellency of the article treated with this composition is more excellent.

[0309] The proportion of monomer (c) contained in the mixture is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and still more preferably 1 to 10% by mass, relative to the total mass of the monomers constituting the non-fluorine polymer. When the proportion of monomer (c) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the proportion of monomer (c) is at most the above upper limit value, the polymerization yield is good, non-fluorine polymer (A) can sufficiently contain the units based on monomer (a) and monomer (b), and the water repellency of the article treated with this composition is more excellent.

[0310] The total proportion of monomer (a) and monomer (b) contained in the mixture is preferably 55% by mass or more, more preferably 60 to 98% by mass, and still more preferably 68 to 96% by mass, relative to the total mass of the monomers constituting the non-fluoropolymer. When the total proportion of monomer (a) and monomer (b) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the total proportion of monomer (a) and monomer (b) is at most the above upper limit value, monomer (c) can be sufficiently contained, and the water repellency of the article treated with this composition is more excellent.

[0311] The total proportion of monomer (b) and monomer (c) contained in the mixture is preferably 5.1 to 50% by mass, more preferably 5.5 to 40% by mass, and still more preferably 6 to 30% by mass, relative to the total mass of the monomers constituting the non-fluoropolymer. When the total proportion of monomer (b) and monomer (c) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the total proportion of monomer (b) and monomer (c) is at most the above upper limit value, monomer (a) can be sufficiently contained, and the water repellency of the article treated with this composition is more excellent.

[0312] The total proportion of monomer (c) and monomer (a) contained in the mixture is preferably 50.1 to 95% by mass, more preferably 55 to 90% by mass, and still more preferably 60 to 90% by mass, relative to the total mass of the monomers constituting the non-fluoropolymer. When the total proportion of monomer (c) and monomer (a) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the total proportion of monomer (c) and monomer (a) is at most the above upper limit value, monomer (b) can be sufficiently contained, and the water repellency of the article treated with this composition is more excellent.

[0313] The mass ratio of monomer (a) / monomer (b) contained in the mixture is preferably 1.6 to 19, more preferably 2.2 to 18, and still more preferably 3 to 10. When the mass ratio of monomer (a) / monomer (b) is at least the above lower limit value, the water repellency 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 easily carried out during the production of polymer (A).

[0314] The mass ratio of monomer (b) / monomer (c) contained in the mixture is preferably 0.25 to 300, more preferably 0.3 to 50, and still more preferably 0.8 to 20. When the mass ratio of monomer (b) / monomer (c) is at least the above lower limit value, the water repellency 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 easily carried out during the production of polymer (A).

[0315] The mass ratio of monomer (c) / monomer (a) contained in the mixture is preferably from 0.001 to 0.4, more preferably from 0.005 to 0.27, and still more preferably from 0.01 to 0.17. When the mass ratio of monomer (c) / monomer (a) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the mass ratio of monomer (c) / monomer (a) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0316] The mass ratio of {monomer (a) + monomer (b)} / monomer (c) contained in the mixture is preferably from 2.75 to 950, more preferably from 4 to 800, and still more preferably from 6 to 200. When the mass ratio of {monomer (a) + monomer (b)} / monomer (c) is at least the above lower limit value, the water repellency of the article treated with this composition is more excellent. When the mass ratio of {monomer (a) + 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).

[0317] When the mixture contains monomer (d), the proportion of monomer (d) contained in the mixture is preferably from 0.1 to 15% by mass, more preferably from 0.2 to 10% by mass, and still more preferably from 0.5 to 6% by mass, relative to the total mass of the monomers constituting the non-fluoropolymer.

[0318] When the mixture contains monomer (e), the proportion of monomer (e) contained in the mixture is preferably from 0.1 to 15% by mass, more preferably from 0.2 to 10% by mass, and still more preferably from 0.5 to 6% by mass, relative to the total mass of the monomers constituting the non-fluoropolymer.

[0319] When the mixture contains monomer (d) or monomer (e), the total proportion of monomer (d) and monomer (e) contained in the mixture is preferably from 0.2 to 30% by mass, more preferably from 0.4 to 20% by mass, and still more preferably from 1 to 12% by mass, relative to the total mass of the monomers constituting the non-fluoropolymer.

[0320] Examples of the polymerization method of the monomer components include emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method, etc. Among these, the emulsion polymerization method is preferred. By polymerizing the monomer components by the emulsion polymerization method, the molecular weight (Mn, Mw) of polymer (A) can be increased.

[0321] In the emulsion polymerization method, for example, the above-mentioned 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.

[0322] Examples of the medium, surfactant, polymerization initiator, and molecular weight regulator are the same as those described above.

[0323] With respect 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.

[0324] The emulsion can be prepared by mixing a medium, a monomer component, and a surfactant as needed, dispersing them using a homogenizer, a high-pressure emulsifier, etc., and then adding a 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.

[0325] The concentration of the monomer component in the emulsion is preferably 5 to 60% by mass, more preferably 10 to 50% by mass. When the concentration of the monomer component in the emulsion is within the aforementioned range, the molecular weight of the polymer (A) can be sufficiently increased.

[0326] The content of the surfactant in the emulsion is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the monomer component. When the content of the surfactant is at least the aforementioned lower limit value, the dispersion stability of the emulsion is excellent. When the content of the surfactant is at most 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.

[0327] The content of the polymerization initiator in the emulsion is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the monomer component. When the content of the polymerization initiator is at least 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 at most the aforementioned upper limit value, a polymer having a molecular weight in a desired range can be easily obtained.

[0328] By polymerizing the monomer component in the emulsion, a dispersion of the polymer (A) is thereby obtained.

[0329] In the dispersion, the polymer (A) is dispersed in the aqueous medium in the form of emulsion particles.

[0330] In the dispersion, the average particle diameter of the emulsion particles of the 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 most the aforementioned upper limit value, the water repellency of the article treated with the emulsion particles of the polymer (A) and the dispersibility of the emulsion particles of the polymer (A) are more excellent. When the average particle diameter is at least the aforementioned lower limit value, the emulsion particles of the polymer (A) are more stable to mechanical shear force.

[0331] Regarding the average particle diameter of the emulsion particles of the polymer (A), it is calculated by analyzing the autocorrelation function obtained by the dynamic light scattering method for a sample obtained by diluting the dispersion of the polymer (A) with water to a solid content concentration of 1% by mass by the cumulant method.

[0332] The dispersion of the polymer (A) obtained by polymerizing the monomer components in an emulsion can be used directly as the present composition, or can be diluted with an aqueous medium to adjust the solid content concentration and then used as the present composition. Other components can also be added to the present composition.

[0333] <Treatment method of the water repellent composition>

[0334] The treatment method of the present embodiment is a treatment method using the present composition. Any method that can attach the present composition to the article to be treated can be used. For example, when the present composition contains a liquid medium, methods such as coating, impregnation, dipping, spraying, brushing, filling, size press, and rollers can be used to treat the article with the present dispersion and then dry it.

[0335] 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.

[0336] The amount of the 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.

[0337] 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. In addition, when the water repellent composition contains a crosslinking agent, if necessary, it is preferably heated to a temperature above the crosslinking temperature of the crosslinking agent for curing.

[0338] <Article>

[0339] The article of the present embodiment is an article treated with the present composition.

[0340] Examples of the article treated with the present composition include fibers, fiber fabrics (fiber woven fabrics, fiber knitted fabrics, non-woven fabrics, fleece fabrics, etc.), fiber products having a fiber fabric (clothing 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.

[0341] As the article to be treated, fibers, fiber cloths, and fiber products having fiber cloths are preferred. The type of fiber is not particularly limited, and examples thereof 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. As the fiber in the case where the fiber substrate is a nonwoven fabric, examples thereof include polyethylene, polypropylene, polyolefin, polyethylene terephthalate, polytetrafluoroethylene, glass, and rayon.

[0342] The thickness of the fiber cloth is not particularly limited, but is 10 μm to 5 cm.

[0343] (Mechanism of Action)

[0344] For the present composition described above, since the polymer (A) has units (a), units (b) and units (c), the water repellency of the articles treated with the present composition is excellent. In addition, its water repellency is not easily reduced by washing, so the washing durability of the articles treated with the present composition is excellent. The mechanism for exerting this effect is considered to be as follows. Monomer (a) and monomer (b) are compounds having one (meth) acryloyl group, so it is believed that the polymerization is carried out one-dimensionally. On the other hand, monomer (c) is a compound having two or more (meth) acryloyl groups, so it is believed that the polymerization is carried out two-dimensionally, and three-dimensionally according to the situation. That is, it is expected that by having a structural unit based on monomer (c), the polymer becomes a dense structure. It is believed that this dense structure contributes to the improvement of water repellency and washing durability.

[0345] Example

[0346] Hereinafter, the present invention will be described in detail by way of Examples, but the present invention is not limited thereto. "Parts" means "parts by mass".

[0347] Examples 1 to 11, 16 to 26 and 29 are embodiments, and Examples 12 to 15, 27 and 28 are comparative examples.

[0348] <Ratio of Monomer Units>

[0349] The composition of the polymer (the ratio of each monomer unit to all units constituting the polymer) is calculated based on the charged amounts of the monomer components.

[0350] <Molecular weight of polymer>

[0351] The molecular weight of the polymer recovered by the following recovery method was measured.

[0352] (Polymer Recovery)

[0353] 20 g of tetrahydrofuran (THF) was added to 10 g of the polymer emulsion and stirred. The mixture was concentrated to 8 g under reduced pressure. The concentrated solution was added dropwise to a beaker containing 30 g of methanol with stirring to precipitate the polymer. The supernatant was removed by decantation and vacuum dried overnight at 35 °C to obtain the polymer.

[0354] <Measurement of molecular weight>

[0355] The recovered polymer was made into a 1% THF solution, passed through a filter with a pore size of 0.45 μm to prepare an analysis sample. The number average molecular weight (Mn) and weight average molecular weight (Mw) of this sample were measured under the following measurement conditions. The measurement conditions are as follows.

[0356] Apparatus: TOSOH EcoSEC HLC-8320GPC, manufactured by Tosoh Corporation,

[0357] Column: A column formed by connecting Shodex GPC KF-802 (8.0 mm I.D. × 300 mm) and KF-806M (8.0 mm I.D. × 300 mm) in series,

[0358] Measurement temperature: 40 °C,

[0359] Injection volume: 30 μL,

[0360] Elution rate: 1.0 ml / min,

[0361] Eluent: THF,

[0362] Standard sample: EasiCal PS-2, manufactured by Polymer laboratories.

[0363] <Water repellent treatment of fabrics>

[0364] For the emulsion obtained in the polymerization example described below, the following method was used to process the fabric to obtain a water repellent treated fabric. The emulsion and blocked isocyanate (MEIKANATE TP-10, manufactured by Meisei Chemical Industry Co., Ltd.) as a crosslinking agent were diluted with distilled water to prepare a water repellent composition. The dyed nylon fabric and polyester fabric were immersed in this water repellent composition and squeezed evenly. After drying for 90 seconds at 110 °C using a stenter, heat treatment was further carried out at 170 °C for 90 seconds.

[0365] <Water repellency evaluation (initial)>

[0366] For the test cloth, the water repellency was evaluated according to the spray test of JIS L 1092-2009. The water repellency is expressed by grades from 1 to 5. The larger the score, the better the water repellency. When +(-) is marked in the grade, it means that each property is slightly better (worse) compared with the standard substance of the aforementioned grade.

[0367] <Evaluation of washing durability (after washing)>

[0368] For the test cloth, according to the C4M water washing method specified in Appendix F of JIS L 1930 [Specification of washing method for C-type standard washing machine (agitator type)], washing was repeated 20 times. After washing, drying was carried out using a tumble dryer, and after air-drying overnight in a room at 25 °C and 60% humidity, the aforementioned water repellency was evaluated.

[0369] <Comprehensive evaluation>

[0370] Regarding Examples 16 to 29, 3 was set as 3 points, 3+ was set as 3.2 points, 4- was set as 3.8 points, 4 was set as 4 points, and the sum of the initial evaluation of the polyester fabric, the evaluation after washing, the initial evaluation of the nylon fabric, and the evaluation after washing was used as the comprehensive evaluation.

[0371] The compound names described in this specification are as follows.

[0372] Monomer (a):

[0373] BeA: behenyl acrylate

[0374] StA: stearyl acrylate

[0375] Monomer (b):

[0376] VdCl: vinylidene chloride

[0377] Monomer (c):

[0378] 16HDA: 1,6-hexanediol diacrylate

[0379] 110DDA: 1,10-decanediol diacrylate

[0380] 16HDMA: 1,6-hexanediol dimethacrylate

[0381] TMP3A: trimethylolpropane triacrylate

[0382] TMP3MA: trimethylolpropane trimethacrylate

[0383] DTMP4A: bis(trimethylolpropane) tetraacrylate

[0384] DPE6A: dipentaerythritol hexaacrylate

[0385] BPA2M: Bisphenol A dimethacrylate

[0386] ICN3A: Tris(2-acryloyloxyethyl) isocyanurate

[0387] 1353ATA: 1,3,5-Triacryloyl hexahydro-1,3,5-triazine

[0388] NNMBAA: N,N'-Methylenebisacrylamide

[0389] NNMBMA: N,N'-Methylenebismethacrylamide

[0390] Monomer (d):

[0391] D-BP: 3,5-Dimethylpyrazole adduct of isocyanatoethyl acrylate

[0392] Monomer (e):

[0393] DMAA: Dimethylacrylamide

[0394] Surfactant:

[0395] E420: Polyoxyethylene oleyl ether (Emulgen (trade name of Kao Corporation) 420, about 13 moles of ethylene oxide adduct)

[0396] P204: Ethylene oxide-propylene oxide polymer (trade name of NOF Corporation, Plonon 204, the proportion of ethylene oxide is 40% by mass.)

[0397] TMAC: Solution of 63% stearyl trimethyl ammonium chloride, 32% isopropyl alcohol and 5% water (manufactured by LION SPECIALTY CHEMICALS CO., Ltd.)

[0398] Molecular weight regulator:

[0399] StSH: Stearyl mercaptan

[0400] Polymerization initiator:

[0401] VA-061A: Acetate of 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (manufactured by Wako Pure Chemical Industries, Ltd., VA-061)

[0402] Medium:

[0403] DPG: Dipropylene glycol

[0404] Water

[0405] (Polymerization Example 1)

[0406] (Manufacture of polymer emulsion)

[0407] Put 72 parts by mass of StA, 4 parts by mass of 16HDA, 4 parts by mass of MOI-BP, 2.5 parts by mass of E420, 2.5 parts by mass of P204, 0.5 parts by mass of TMAC, 4 parts by mass of StSH, 155 parts by mass of water, and 30 parts by mass of DPG into a glass beaker. After heating at 60 °C for 30 minutes, use a homogenizer (manufactured by Nippon Seiki Co., Ltd., BioMixer) to mix and obtain a mixed solution.

[0408] While maintaining the above mixed solution at 60 °C, use a high-pressure emulsifier (manufactured by APV Rannie Co., Ltd., Mini Labo) to process it at 40 MPa to obtain an emulsion. Put this emulsion into a stainless steel reactor and cool it to 40 °C or lower. Add 20 parts by mass of VdCl and 0.5 parts by mass of VA061A to it. After replacing the gas phase with nitrogen, carry out a polymerization reaction at 60 °C with stirring for 15 hours to obtain a polymer emulsion. The solid content concentration is 36.8% by mass.

[0409] (Polymerization Example 2-15)

[0410] Change to the input ratio shown in Table 1. Except for this, operate in the same manner as in Polymerization Example 1 to obtain the polymer emulsion of Polymerization Example 2-15. The solid content concentration of the obtained emulsion is also shown in Table 1.

[0411] (Example 1-15)

[0412] Process the emulsion obtained in Polymerization Examples 1-15 according to the water repellent treatment of the above fabric at a solid content of 1% by mass, and evaluate the obtained processed fabric according to its water repellency. The evaluation results are shown in Table 1. Compared with Examples 1-11 using monomer (a), monomer (b), and monomer (c), and Examples 12-15 using monomer (a) and not using either or both of monomer (b) and monomer (c), good water repellency can be obtained.

[0413] (Polymerization Examples 16-29)

[0414] Change to the input ratio shown in Table 2. Except for this, operate in the same manner as in Polymerization Example 1 to obtain the polymer emulsion of Polymerization Examples 16-29. The solid content concentration of the obtained emulsion is also shown in Table 2.

[0415] (Examples 16-29)

[0416] The emulsions obtained in Polymerization Examples 16 - 29 were processed according to the water repellency treatment of the above-mentioned fabric at 1% by mass of the solid content, and the resulting processed fabric was evaluated for water repellency. The evaluation results are shown in Table 2. Compared with Examples 27 - 28 using monomers (a) and (b) without using monomer (c), Examples 16 - 26 and 29 using monomers (a), (b), and (c) can obtain good water repellency and washing durability of water repellency.

[0417] [Table 1]

[0418]

[0419] [Table 2]

[0420]

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, and a structural unit based on a monomer having two or more (meth)acryloyl groups.

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 (1), R 2 -OC(=O)CR 1 =CH2 (1) In the formula (1), R 1 represents H, CH3 or a chlorine atom, and R 2 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 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 (1) and the structural unit of the (meth)acrylic acid long-chain alkyl ester monomer with 19 to 30 carbon atoms based on R in the formula (1). 2 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 (1) and the structural unit of the (meth)acrylic acid long-chain alkyl ester monomer with 19 to 30 carbon atoms based on R in the formula (1). 2 The structural unit of the (meth)acrylic acid long-chain alkyl ester monomer with 19 to 30 carbon atoms based on R in the formula (1).

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 12 to 18 carbon atoms in R in the formula (1) is 1 to 45% by mass. 2 ​ 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 monomer having two or more (meth)acryloyl groups is represented by the following formula (2), Q-(R 4 C(=O)CR 3 =CH2) n (2) In the formula (2), n represents an integer from 2 to 10, and R 3 represents H, CH3, or a chlorine atom, and R 4 represents a single bond or a divalent organic group. Q represents a linear or branched alkylene group having 1 to 16 carbon atoms, a residue obtained by removing hydrogen from a hydroxyl group of a polyol, a trivalent group represented by the formula (3), or a trivalent group represented by the formula (4). The plurality of (R 4 C(=O)CR 3 =CH2) may be the same or different. In the formula (3) and the formula (4), * represents a connecting bond. When Q is a linear or branched alkylene group having 1 to 16 carbon atoms or a residue obtained by removing hydrogen from a hydroxyl group of a polyol, the atom in R 4 bonded to Q is an atom other than an oxygen atom.

7. The water repellent composition according to claim 1, wherein, 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 50 to 90% by mass, the proportion of the structural unit based on the vinyl halide monomer is 5 to 30% by mass, and the proportion of the structural unit based on the monomer having two or more (meth)acryloyl groups is 0.1 to 20% by mass.

8. A method for manufacturing a non-fluorine polymer, which polymerizes a mixture containing a long-chain alkyl (meth)acrylate monomer, a vinyl halide monomer, and a monomer having two or more (meth)acryloyl groups in the presence of a surfactant and a polymerization initiator, wherein, With respect to the total mass of the monomers constituting the non-fluoropolymer, the proportion of the (meth)acrylic acid long-chain alkyl ester monomer is 50 to 90% by mass, the proportion of the vinyl halide monomer is 5 to 30% by mass, and the proportion of the monomer having two or more (meth)acryloyl groups is 0.1 to 20% by mass.

9. The method for manufacturing a non-fluorine polymer according to claim 8, wherein, Furthermore, the polymerization is carried out in the presence of a molecular weight regulator.

10. The method for manufacturing a non-fluorine polymer according to claim 9, wherein, With respect to 100 parts by mass of all the monomers constituting the non-fluoropolymer, the proportion of the molecular weight regulator is 0.1 to 20 parts by mass.

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

12. An article obtained by treating with the water repellent composition according to any one of claims 1 to 7.

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