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

Abstract

The present invention relates to a water repellent composition comprising a non-fluoropolymer 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 (meth) acrylate monomer having a polysiloxane structure, the molecular weight of the (meth) acrylic acid ester monomer having a polysiloxane structure is 1000-3600, and the ratio of structural units based on a halogenated ethylene monomer to the total amount of structural units of the non-fluoropolymer is 1-12 mass%.

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. 2022-186729 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 fluoropolymer used in the above method from the viewpoint of high environmental burden. Therefore, 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 is required.

[0004] As a water repellent composition containing a non-fluoropolymer, for example, Patent Document 1 discloses a water repellent composition containing a non-fluorocopolymer, which is characterized in that it contains: a structural unit based on a (meth)acrylate monomer (A) having no polyfluoroalkyl group and 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 the monomer (A) is 5 to 95% by mass among all structural units (100% by mass), the proportion of the structural unit based on the monomer (B) is 5 to 60% by mass among all structural units (100% by mass), and the total content ratio of the structural unit based on the monomer (A) and the structural unit based on the 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: International Publication No. 2009 / 113589 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] When the content of the non-fluoropolymer in the water repellent composition is low, good water repellency may not be exhibited. In addition, when an article subjected to water repellent treatment is used for a long time, a problem of durability such as a decrease in water repellency may occur. In the water repellent composition described in Patent Document 1, when the content of the non-fluoropolymer is low, the water repellency and durability are insufficient. Therefore, a water repellent composition containing a non-fluorocopolymer that can obtain sufficient water repellency and durability even when the content of the non-fluoropolymer in the water repellent composition is low is sought.

[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 aforementioned water repellent composition, and an article with excellent water repellency treated with the aforementioned water repellent composition.

[0011] Means for solving the problems

[0012] The present invention has the following aspects.

[0013] [1] A water repellent composition comprising a non-fluoropolymer having a structural unit based on a (meth)acrylic long-chain alkyl ester monomer, a structural unit based on a vinyl halide monomer, and a structural unit based on a (meth)acrylate monomer having a polysiloxane structure, wherein the molecular weight of the aforementioned (meth)acrylate monomer having a polysiloxane structure is 1000 to 3600, 1200 to 3500, or 1500 to 3300, and the proportion of the structural unit based on the vinyl halide monomer relative to the total amount of the structural units of the aforementioned non-fluoropolymer is 1 to 12% by mass, 2 to 11% by mass, or 3 to 10% by mass.

[0014] [2] The water repellent composition according to [1], wherein the total proportion of the aforementioned structural unit based on the (meth)acrylic long-chain alkyl ester monomer, the aforementioned structural unit based on the vinyl halide monomer, and the aforementioned structural unit based on the (meth)acrylate monomer having a polysiloxane structure relative to the total amount of the structural units of the aforementioned non-fluoropolymer is 80% by mass or more, 80 to 99% by mass, or 82 to 98% by mass.

[0015] [3] The water repellent composition according to [1] or [2], wherein the aforementioned vinyl halide monomer is vinyl chloride or vinylidene chloride.

[0016] [4] The water repellent composition according to any one of [1] to [3], wherein the aforementioned (meth)acrylate monomer having a polysiloxane structure is represented by the following formula (1) or formula (2).

[0017] R 1 -(Si(R 2 )2O) m -Si(R 2 )2-R 3 OC(=O)CR 4 =CH2 (1)

[0018] In the aforementioned formula (1), R 1 represents a monovalent hydrocarbon group having 1 to 12, 1 to 10, 1 to 8, or 1 to 6 carbon atoms; R 2 represents H or CH3, preferably CH3, R 3represents a divalent hydrocarbon group having 1 to 6, 1 to 4 or 1 to 3 carbon atoms; R 4 represents H, CH3 or a chlorine atom, preferably H or CH3, more preferably CH3; m represents an integer of 8 to 55, an integer of 10 to 45, an integer of 12 to 43 or an integer of 16 to 40; a plurality of R 2 are optionally the same or different, preferably the same.

[0019] CH2=CR 5 C(=O)OR 6 -(Si(R 7 )2O) n -Si(R 7 )2-R 6 OC(=O)CR 5 =CH2 (2)

[0021] In the foregoing formula (2), R 5 represents H, CH3 or a chlorine atom, preferably H or CH3, more preferably CH3; R 6 represents a divalent hydrocarbon group having 1 to 6, 1 to 4 or 1 to 3 carbon atoms; R 7 represents H or CH3, preferably CH3; n represents an integer of 8 to 55, an integer of 10 to 45, an integer of 12 to 43 or an integer of 16 to 40; a plurality of R 5 are optionally the same or different, preferably the same; a plurality of R 6 are optionally the same or different, preferably the same; a plurality of R 7 are optionally the same or different, preferably the same.

[0022] [5] The water repellent composition according to any one of [1] to [4], wherein the long-chain alkyl (meth)acrylate monomer is represented by the following formula (3).

[0023] R 9 -OC(=O)CR 8 =CH2 (3)

[0024] In the foregoing formula (3), R 8 represents H, CH3 or a chlorine atom, preferably H or CH3, more preferably H; R 9 represents an alkyl group having 12 to 30, 14 to 28 or 16 to 24 carbon atoms.

[0025] [6] The water repellent composition according to [5], wherein the structural unit based on the long-chain alkyl (meth)acrylate monomer comprises a structural unit of a long-chain alkyl (meth)acrylate monomer having 12 to 18, 16 to 18 or 18 carbon atoms based on R 9 in the foregoing formula (3) and a structural unit based on R9 a structural unit of a long-chain alkyl (meth)acrylate monomer having 19 to 30, 20 to 28, or 20 to 24 carbon atoms.

[0026] [7] The water repellent composition according to [6], wherein, based on R in the aforementioned formula (3) 9 the total proportion of the structural units of the long-chain alkyl (meth)acrylate monomer having 19 to 30, 20 to 28, or 20 to 24 carbon atoms relative to the total amount of the structural units based on the long-chain alkyl (meth)acrylate monomer is 50 to 99% by mass, 55 to 99% by mass, 60 to 95% by mass, or 62 to 90% by mass.

[0027] [8] The water repellent composition according to any one of [1] to [7], wherein the aforementioned non-fluoropolymer further has a structural unit based on a crosslinkable monomer, and the proportion of the structural unit based on the crosslinkable monomer relative to the total amount of the structural units of the non-fluoropolymer is preferably 0.1 to 15% by mass, more preferably 0.2 to 10% by mass, and further preferably 0.5 to 6% by mass.

[0028] [9] A method for producing a non-fluoropolymer, wherein a mixture containing a long-chain alkyl (meth)acrylate monomer, a vinyl halide monomer, and a (meth)acrylate monomer having a polysiloxane structure is polymerized in the presence of a surfactant and a polymerization initiator. The proportion of the long-chain alkyl (meth)acrylate monomer is 73 to 95% by mass, 74 to 92% by mass, or 75 to 90% by mass relative to the total mass of all the monomers constituting the non-fluoropolymer, the proportion of the vinyl halide monomer is 1 to 12% by mass, 2 to 11% by mass, or 3 to 10% by mass, and the proportion of the (meth)acrylate monomer having a polysiloxane structure is 0.5 to 15% by mass, 0.8 to 14% by mass, or 1 to 13% by mass.

[0029]

[10] A treatment method using the water repellent composition according to any one of [1] to [8].

[0030]

[11] An article obtained by treating with the water repellent composition according to any one of [1] to [8].

[0031] Effects of the Invention

[0032] According to the present invention, there can be provided 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 aforementioned water repellent composition, and a water repellent excellent article treated with the aforementioned water repellent composition. Detailed Embodiments

[0033] The meanings and definitions of the terms in this specification are as follows.

[0034] "Non-fluorinated polymer" 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.

[0035] "Structural unit based on monomer" is a general term for atomic groups directly formed by polymerizing one molecule of monomer and atomic groups obtained by chemically converting a part of the aforementioned atomic groups.

[0036] "(Meth)acrylate" is a general term for acrylate, methacrylate, and compounds obtained by substituting the methyl group in the methacryloyl group of the aforementioned methacrylate with a chlorine atom. Similarly, "(meth)acryloyl" is a general term for acryloyl, methacryloyl, and groups obtained by substituting the methyl group in the methacryloyl group with a chlorine atom.

[0037] "Long-chain alkyl" means an alkyl group having 12 or more carbon atoms.

[0038] "Vinyl halide" is a compound in which at least one hydrogen atom in ethylene is substituted with a halogen atom.

[0039] "Having a polysiloxane structure" means that the polymer has a repeating unit represented by "-(Si(R)2O) x1 -". R represents H or CH3, and x1 is an integer of 5 or more. Multiple Rs may be the same or different.

[0040] The molecular weight of a (meth)acrylate monomer having a polysiloxane structure can be calculated using the measurement result of the (meth)acryloyl equivalent (the number of molecules of methacryloyl per unit mass). When the structure of the (meth)acrylate monomer having a polysiloxane structure is known, it is the formula weight.

[0041] The number-average molecular weight (hereinafter also denoted as "Mn") and weight-average molecular weight (hereinafter also denoted as "Mw") of the polymer are polystyrene-converted molecular weights obtained by using a standard curve prepared with a standard polystyrene sample and measuring by gel permeation chromatography (hereinafter also denoted as "GPC").

[0042] The solid content concentration is calculated as follows: Let the mass of the sample before heating be the sample mass, and the mass of the sample after drying in a convection dryer at 120 °C for 4 hours be the solid content mass, and calculate using (solid content mass / sample mass) × 100.

[0043] "~" indicating a numerical range means including the values described before and after as the lower limit value and the upper limit value.

[0044] Water-repellent agent composition

[0045] The water-repellent agent composition of this embodiment (hereinafter also referred to as "this composition") contains a specific polymer (hereinafter also referred to as "polymer (A)"). Polymer (A) is a non-fluoropolymer, and the non-fluoropolymer has a structural unit based on a (meth)acrylic 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 (meth)acrylate monomer having a polysiloxane structure with a molecular weight of 1000 to 3600 (hereinafter also referred to as "monomer (c)"). The proportion of the structural unit based on monomer (b) relative to the total amount of the structural units of polymer (A) is 1 to 12% by mass. Polymer (A) may contain either or both of the structural unit based on monomer (d) and the structural unit based on monomer (e) described below.

[0046] This composition may contain polymer (A) and a medium.

[0047] This composition may contain one or more selected from the group consisting of a surfactant, a molecular weight regulator, and a polymerization initiator.

[0048] This composition may contain other components as needed.

[0049] This composition is preferably a non-fluoropolymer solution containing polymer (A). The non-fluoropolymer solution also includes: a dispersion obtained by the manufacturing method described below, and a dispersion further diluted with an arbitrary medium for treating an article.

[0050] This composition may be a non-fluoropolymer solution, which contains polymer (A) and an organic solvent as a medium and does not contain a surfactant.

[0051] <Polymer (A)>

[0052] 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)").

[0053] Polymer (A) may further have either or both of a unit based on monomer (d) (hereinafter also referred to as "unit (d)") and a unit based on monomer (e) (hereinafter also referred to as "unit (e)") as needed.

[0054] (Monomer (a))

[0055] The monomer (a) is a long-chain alkyl (meth)acrylate monomer. The long-chain alkyl (meth)acrylate is a monomer having an alkyl group with 12 or more carbon atoms and one (meth)acryloyl group in one molecule.

[0056] As the monomer (a), a long-chain alkyl (meth)acrylate monomer represented by the following formula (3) is preferred.

[0057] R 9 -OC(=O)CR 8 =CH2 (3)

[0058] In the above formula (3), R 8 represents H, CH3 or a chlorine atom, and R 9 represents an alkyl group having 12 to 30 carbon atoms.

[0059] R 8 is preferably H or CH3, more preferably H.

[0060] The long-chain alkyl group may be straight-chain or branched-chain, and is preferably straight-chain.

[0061] R 9 preferably has 12 to 30 carbon atoms, more preferably 14 to 28 carbon atoms, and further preferably 16 to 24 carbon atoms. If the number of carbon atoms is at least the aforementioned lower limit value, the water repellency is excellent. If the number of carbon atoms is at most the aforementioned upper limit value, the availability and processability are excellent.

[0062] As the monomer (a), lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate are preferred.

[0063] In addition, two or more kinds of the monomer (a) can be used in combination. As the monomer (a), a combination of a long-chain alkyl (meth)acrylate monomer in which R 9 in the above formula (3) has 12 to 18 carbon atoms (hereinafter also referred to as "monomer (a1)") and a long-chain alkyl (meth)acrylate monomer in which R 9 in the above formula (3) has 19 to 30 carbon atoms (hereinafter also referred to as "monomer (a2)") is particularly preferred.

[0064] The monomer (a1) may be a mixture of any two or more of the long-chain alkyl (meth)acrylate monomers in which R 9 in the above formula (3) has 12 to 18 carbon atoms. The monomer (a2) may be a mixture of any two or more of the long-chain alkyl (meth)acrylate monomers in which R 9 in the above formula (3) has 19 to 30 carbon atoms.

[0065] The alkyl group of the monomer (a1) has 12 to 18 carbon atoms, preferably 16 to 18 carbon atoms, and more preferably 18 carbon atoms. When the number of carbon atoms is at least the lower limit value, the water repellency is excellent. When the number of carbon atoms is at most the upper limit value, the availability and processability are excellent.

[0066] The alkyl group of the monomer (a2) has 19 to 30 carbon atoms, preferably 20 to 28 carbon atoms, and more preferably 20 to 24 carbon atoms. When the number of carbon atoms is at least the lower limit value, the water repellency is excellent. When the number of carbon atoms is at most the upper limit value, the availability and processability are excellent.

[0067] When the monomers (a1) and (a2) are used in combination, the proportion of the structural unit based on the monomer (a1) relative to the total amount of the structural units based on the monomer (a) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 10 to 38% by mass. When the said proportion is at least the lower limit value, the initial water repellency becomes better. When the said proportion is at most the upper limit value, the water repellency after washing becomes better.

[0068] When the monomers (a1) and (a2) are used in combination, the proportion of the structural unit based on the monomer (a2) relative to the total amount of the structural units based on the monomer (a) is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and further preferably 62 to 90% by mass. When the said proportion is at least the lower limit value, the initial water repellency becomes better. When the said proportion is at most the upper limit value, the water repellency after washing becomes better.

[0069] 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) relative to the total amount of the structural units based on the monomer (a) is preferably 70% by mass or more, more preferably 72% by mass or more, further preferably 75% by mass or more, particularly preferably 85% by mass or more, and may be 100% by mass. When the said proportion is at least the lower limit value, the initial water repellency becomes good. When the said proportion is at most the upper limit value, the water repellency after washing becomes better.

[0070] When the structural unit based on the monomer (a1) and the structural unit based on the monomer (a2) are used in combination, the mass ratio of the structural unit based on the monomer (a1) relative to the total amount of the structural unit based on the monomer (a1) and the structural unit based on the monomer (a2) is preferably 1 / 99 to 50 / 50, more preferably 5 / 95 to 40 / 60, and further preferably 10 / 90 to 38 / 62. When the said mass ratio is at least the lower limit value, the water repellency of the treated article is likely to become good. When the said mass ratio is at most the upper limit value, the washing durability of the treated article is likely to become good.

[0071] (Monomer (b))

[0072] Monomer (b) is a vinyl halide. As monomer (b), vinyl halides having 1 or 2 halogen atoms are preferred, and vinylidene halides having 2 halogen atoms are more preferred.

[0073] The halogen atoms of the aforementioned vinyl halide are preferably chlorine atoms, bromine atoms, iodine atoms, more preferably chlorine atoms and bromine atoms, and further preferably chlorine atoms. In addition, when the aforementioned vinyl halide has 2 or more halogen atoms, the plurality of halogen atoms may be the same or different.

[0074] As monomer (b), vinyl chloride or vinylidene chloride is preferred.

[0075] Two or more kinds of monomer (b) can be used in combination.

[0076] By having unit (b), the adhesion of the polymer (A) to the article to be treated is improved, and the durability is improved. Furthermore, it is easy to form a dense water-repellent film on the surface of the article, and the water repellency is also improved.

[0077] (Monomer (c))

[0078] Monomer (c) is a (meth)acrylate monomer having a polysiloxane structure with a molecular weight of 1000 to 3600. By making the polymer (A) have unit (c), the water repellency and the water repellency of the water-repellent film formed on the surface of the article to be treated are improved. The molecular weight of monomer (c) is 1000 to 3600, preferably 1200 to 3500, and more preferably 1500 to 3300. If the molecular weight is above the lower limit value of the aforementioned range, unit (c) is likely to be exposed on the surface of the aforementioned water-repellent film, and the water repellency is improved. If the molecular weight is below the upper limit value of the aforementioned range, the viscosity of the water repellent composition will not become too high, and the water repellency and the water repellency of the aforementioned water-repellent film are improved.

[0079] Monomer (c) has 1 or more (meth)acryloyl groups, preferably 1 to 4, and more preferably 1 to 2.

[0080] Monomer (c) may have a functional group capable of crosslinking described later.

[0081] As monomer (c), a (meth)acrylate monomer having a polysiloxane structure represented by the following formula (1) or (2) is preferred.

[0082] R 1 -(Si(R 2 )2O) m -Si(R 2 )2-R 3 OC(=O)CR 4 =CH2 (1)

[0083] In the above formula (1), R 1 represents a monovalent hydrocarbon group having 1 to 12 carbon atoms; R 2 represents H or CH3; R 3 represents a divalent hydrocarbon group having 1 to 6 carbon atoms; R 4 represents H, CH3 or a chlorine atom; m represents an integer of 8 to 55; a plurality of R 2 are optionally the same or different.

[0084] CH2=CR 5 C(=O)OR 6 -(Si(R 7 )2O) n -Si(R 7 )2-R 6 OC(=O)CR 5 =CH2(2)

[0085] In the above formula (2), R 5 represents H, CH3 or a chlorine atom; R 6 represents a divalent hydrocarbon group having 1 to 6 carbon atoms; R 7 represents H or CH3; n represents an integer of 8 to 55; a plurality of R 5 are optionally the same or different; a plurality of R 6 are optionally the same or different; a plurality of R 7 are optionally the same or different.

[0086] R 1 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms.

[0087] As the monovalent hydrocarbon group of R 1 , a monovalent saturated hydrocarbon group and a monovalent unsaturated hydrocarbon group can be exemplified. As the monovalent unsaturated hydrocarbon group, a group obtained by replacing one or more carbon-carbon single bonds in the monovalent saturated hydrocarbon group with a carbon-carbon double bond or a triple bond can be exemplified. R 1 is linear, branched or cyclic, and is preferably linear.

[0088] As R 1 , methyl, ethyl, propyl, butyl, hexyl and octyl are preferred.

[0089] R 2 is preferably CH3. A plurality of R in the above formula (1) 2 are preferably the same, and a plurality of R 2 are preferably all CH3.

[0090] R 3 preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms.

[0091] As R 3 The divalent hydrocarbon group, divalent saturated hydrocarbon groups and divalent unsaturated hydrocarbon groups may be exemplified. As the divalent unsaturated hydrocarbon group, a group obtained by replacing one or more carbon-carbon single bonds in the divalent saturated hydrocarbon group with a carbon-carbon double bond or a triple bond may be exemplified. R 3 is linear or branched, preferably linear.

[0092] As R 3 , preferably methylene, ethylene, propylene, trimethylene, hexylene.

[0093] R 4 is preferably H or CH3, more preferably CH3.

[0094] m is preferably 10 to 45, more preferably 12 to 43, and further preferably 16 to 40.

[0095] R 5 is preferably H or CH3, more preferably CH3. A plurality of R's in the aforementioned formula (2) 5 are preferably the same, and two of the plurality of R's 5 are preferably CH3.

[0096] R 6 preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 3 carbon atoms.

[0097] As the divalent hydrocarbon group of R 6 , divalent saturated hydrocarbon groups and divalent unsaturated hydrocarbon groups may be exemplified. As the divalent unsaturated hydrocarbon group, a group obtained by replacing one or more carbon-carbon single bonds in the divalent saturated hydrocarbon group with a carbon-carbon double bond or a triple bond may be exemplified. R 6 is linear or branched, preferably linear.

[0098] As R 6 , preferably methylene, ethylene, propylene, trimethylene, hexylene. A plurality of R's in the aforementioned formula (2) 6 are preferably the same.

[0099] R 7 is preferably CH3. A plurality of R's in the aforementioned formula (2) 7 are preferably the same, and a plurality of R's 7 are preferably all CH3.

[0100] n is preferably 10 to 45, more preferably 12 to 43, and further preferably 16 to 40.

[0101] As the monomer (c), a commercially available product can be used. As the monomer (c) represented by the aforementioned formula (1), R 1 is butyl, R 2 are both CH3, R3 is trimethylene, R 4 is CH3, m is 27, and the compound has a molecular weight of 2300 (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-174BX). As the monomer (c) represented by the foregoing formula (2), examples include R 5 are both CH3, R 6 are both trimethylene, R 7 are both CH3, n is 27, and the compound has a molecular weight of 2370 (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-164C).

[0102] Furthermore, the monomer (c) can also be synthesized by the method described in JP-A-59-78263. Specifically, by using lithium trialkylsilanolate as an initiator, anionic polymerization of a cyclic siloxane is carried out to obtain a living polymer, and further reacting γ-methacryloxypropyl dimethyl monochlorosilane, whereby the monomer (c) represented by the foregoing formula (2) can be obtained.

[0103] (Monomer (d))

[0104] The monomer (d) is a crosslinkable monomer. A crosslinkable monomer refers to a monomer having one functional group capable of crosslinking and a group capable of polymerizing with a (meth)acryloyl group, or a monomer having two or more groups capable of polymerizing with a (meth)acryloyl group. It should be noted that the monomer (d) does not have a polysiloxane structure.

[0105] By making the polymer (A) have a structural unit based on the monomer (d), the washing and rubbing durability is further improved.

[0106] As the group capable of polymerizing with a (meth)acryloyl group, examples include a group having a carbon-carbon double bond at the molecular end, and preferably a (meth)acryloyl group, a vinyl group, or an allyl group.

[0107] As the functional group capable of crosslinking, a functional group having at least one of a covalent bond, an ionic bond, or a hydrogen bond is preferred; or a functional group capable of forming a crosslinked structure by the interaction of the foregoing bonds.

[0108] 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 preferred, and a hydroxyl group, a blocked isocyanate group, a primary amino group, or an epoxy group is particularly preferred.

[0109] As the monomer (d), (meth)acrylates, acrylamides, vinyl ethers having a functional group capable of crosslinking, or vinyl esters having a functional group capable of crosslinking are preferred.

[0110] As the monomer (d), the following compounds can be cited.

[0111] 2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate, 2-butanone oxime adduct of 2-isocyanatoethyl (meth)acrylate (2-(0-(1'-methylpropylideneamino)carboxylamino)ethyl (meth)acrylate), pyrazole adduct of 2-isocyanatoethyl (meth)acrylate, 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate (2-((3,5-dimethylpyrazolyl)carbonylamino)ethyl (meth)acrylate), 3-methylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate, ε-caprolactam adduct of 2-isocyanatoethyl (meth)acrylate, 2-butanone oxime adduct of 3-isocyanatopropyl (meth)acrylate, pyrazole adduct of 3-isocyanatopropyl (meth)acrylate.

[0112] 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.

[0113] Methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, butoxymethyl (meth)acrylamide, diacetone acrylamide, γ-methacryloyloxypropyltrimethoxysilane, trimethoxyvinylsilane, vinyltrimethoxysilane.

[0114] tert-Butyl(methyl)acrylamidosulfonic acid, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, diacetone(meth)acrylamide, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl methacrylate, polyoxyalkylene glycol mono(meth)acrylate, (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyhexahydrophthalic acid, 2-(meth)acryloyloxyethyl acid phosphate, allyl (meth)acrylate, 2-vinyl-2-oxazoline, polycaprolactone ester of 2-vinyl-4-methyl-(2-vinyl oxazoline)hydroxyethyl (meth)acrylate.

[0115] Triallyl isocyanurate (T(M)AIC, manufactured by Nippon Kayaku Co., Ltd.), triallyl cyanurate (TAC, manufactured by Nippon Kayaku Co., Ltd.), 3-(methylethylketoxime)isocyanatomethyl-3,5,5-trimethylcyclohexyl (2-hydroxyethyl methacrylate) cyanate (TECCOAT HE-6P, manufactured by Kyoto Tsutsumakasei Co., Ltd.). Polycaprolactone ester of 2-hydroxyethyl (meth)acrylate (Placcel FA, FM series, manufactured by Daicel Chemical Industries, Ltd.).

[0116] As monomer (d), N-hydroxymethyl(meth)acrylamide, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, 3-chloro-2-hydroxypropyl methacrylate, or polycaprolactone ester of 2-hydroxyethyl (meth)acrylate (Placcel FA, FM series, manufactured by Daicel Chemical Industries, Ltd.), 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate is preferred.

[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 mentioned.

[0120] (Meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid cyclohexyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid n-hexyl ester, (meth)acrylic acid benzyl ester, (meth)acrylic acid octyl ester, methacrylic acid decyl ester, acrylic acid cyclododecyl ester, acrylic acid 3-ethoxypropyl ester, acrylic acid methoxybutyl ester, acrylic acid 2-ethylbutyl ester, acrylic acid 1,3-dimethylbutyl ester, acrylic acid 2-methylpentyl ester.

[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 ethers, haloalkyl vinyl ethers, vinyl alkyl ketones, (meth)acrylic acid aziridinyl ethyl esters, (meth)acrylic acid 2-ethylhexyl polyoxyalkylene esters, bis(meth)acrylic acid polyoxyalkylene esters.

[0124] Alkyl crotonates, alkyl maleates, alkyl fumarates, alkyl citraconates, alkyl mesaconates, triallyl cyanurate, allyl acetate, N-vinylcarbazole, maleimide, N-methylmaleimide, (meth)acrylic acid esters having silicone in the side chain, (meth)acrylic acid esters having a urethane bond, (meth)acrylic acid esters having a polyoxyalkylene chain with an alkyl group having 1 to 4 carbon atoms at the end, alkylene bis(meth)acrylates.

[0125] The total proportion of unit (a), unit (b) and unit (c) relative to all the units constituting polymer (A) is preferably 80% by mass or more, more preferably 80 to 99% by mass, and still more preferably 82 to 98% by mass. If the total proportion of unit (a), 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.

[0126] When the polymer (A) contains either or both of the unit (d) and the unit (e), the total proportion of the unit (a), the unit (b) and the unit (c) relative to all the units constituting the polymer (A) is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0127] The proportion of the unit (a) relative to all the units constituting the polymer (A) is preferably 73 to 95% by mass, more preferably 74 to 92% by mass, and still more preferably 75 to 90% by mass. The proportion of the unit (a) relative to the total amount of the unit (a), the unit (b) and the unit (c) is preferably 73 to 95% by mass, more preferably 75 to 95% by mass, and still more preferably 78 to 94% by mass. If the proportion of the unit (a) is at or above the above lower limit value, the water repellency of the article treated with the present composition is more excellent. If the proportion of the unit (a) is at or below the above upper limit value, the unit (b), the unit (c) and other units can be sufficiently contained, and the water repellency of the article treated with the present composition is more excellent.

[0128] The proportion of the unit (b) relative to all the units constituting the polymer (A) is 1 to 12% by mass, preferably 2 to 11% by mass, and more preferably 3 to 10% by mass. The proportion of the unit (b) relative to the total amount of the unit (a), the unit (b) and the unit (c) is preferably 1 to 12% by mass, more preferably 2 to 11% by mass, and still more preferably 3 to 10% by mass. If the proportion of the unit (b) is at or above the above lower limit value, the water repellency of the article treated with the present composition is more excellent. If the proportion of the unit (b) is at or below the above upper limit value, the unit (a), the unit (c) and other units can be sufficiently contained, and the water repellency of the article treated with the present composition is more excellent.

[0129] The proportion of the unit (c) relative to all the units constituting the polymer (A) is preferably 0.5 to 15% by mass, more preferably 0.8 to 14% by mass, and still more preferably 1 to 13% by mass. If the proportion of the unit (c) relative to the total amount of the unit (a), the unit (b) and the unit (c) is preferably 1 to 15% by mass, more preferably 1 to 14% by mass, and still more preferably 1 to 10% by mass. If the proportion of the unit (c) is at or above the above lower limit value, the water repellency of the article treated with the present composition is more excellent. If the proportion of the unit (c) is at or below the above upper limit value, the unit (a), the unit (b) and other units can be sufficiently contained, and the water repellency of the article treated with the present composition is more excellent.

[0130] The proportion of the total of unit (a) and unit (b) relative to all the units constituting polymer (A) is preferably 70% by mass or more, more preferably 75 - 98% by mass, and still more preferably 80 - 97% by mass. If the proportion of the total 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. If 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.

[0131] The proportion of the total of unit (b) and unit (c) relative to all the units constituting polymer (A) is preferably 4 - 30% by mass, more preferably 5 - 25% by mass, and still more preferably 6 - 22% by mass. If the proportion of the total 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. If 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.

[0132] The proportion of the total of unit (c) and unit (a) relative to all the units constituting polymer (A) is preferably 50.1 - 95% by mass, more preferably 55 - 90% by mass, and still more preferably 60 - 90% by mass. If the proportion of the total 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. If 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.

[0133] The mass ratio of unit (a) / unit (b) is preferably 1.5 - 25, more preferably 2.0 - 24, and still more preferably 3.0 - 23. If 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. If 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).

[0134] The mass ratio of unit (b) / unit (c) is preferably 0.6 - 15, more preferably 0.7 - 13, and still more preferably 0.8 - 12. If 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. If 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).

[0135] The mass ratio of unit (c) / unit (a) is preferably 0.001 to 0.4, more preferably 0.005 to 0.27, and further preferably 0.010 to 0.17. If the mass ratio of unit (c) / unit (a) is above the above lower limit value, the water repellency of the article treated with this composition is more excellent. If the mass ratio of unit (c) / unit (a) is below 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 (a) + unit (b)} / unit (c) is preferably 1.0 to 120, more preferably 1.5 to 110, and further preferably 2.0 to 100. If the mass ratio of {unit (a) + unit (b)} / unit (c) is above the above lower limit value, the water repellency of the article treated with this composition is more excellent. If the mass ratio of {unit (a) + unit (b)} / unit (c) is below the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0137] When polymer (A) contains unit (d), the proportion of unit (d) relative to all the units constituting polymer (A) is preferably 0.1 to 15% by mass, more preferably 0.2 to 10% by mass, and further preferably 0.5 to 6% by mass. If the proportion of unit (d) is above the above lower limit value, the water repellency of the article treated with this composition is more excellent. If the proportion of unit (d) is below the above upper limit value, units (a), (b), (c) and other units can be sufficiently contained, and the water repellency of the article treated with this composition is more excellent.

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

[0139] When the polymer (A) contains the unit (d) or the unit (e), the total proportion of the unit (d) and the unit (e) relative to all the units constituting the polymer (A) 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. If the proportion of the unit (d) and the unit (e) is above the above lower limit value, the water repellency of the article treated with the present composition is more excellent. If the proportion of the unit (d) and the unit (e) is below the above upper limit value, the units (a), (b), and (c) can be sufficiently contained, and the water repellency of the article treated with the present composition is more excellent.

[0140] The proportion of each unit can be calculated based on 1 the reaction rates of the respective monomer components by 1H-NMR, gas chromatography, and high performance liquid chromatography. When manufacturing the polymer (A), when the conversion rate of the monomer components into the polymer (A) is high (for example, 90% or more), the proportion of each unit can be calculated based on the charged amount of the monomer components.

[0141] The Mn of the polymer (A) is preferably 5,000 to 200,000, more preferably 10,000 to 150,000, and still more preferably 20,000 to 120,000. If the Mn of the polymer (A) is above the above lower limit value, the water repellency of the article treated with the present composition is more excellent. If the Mn of the polymer (A) is below the above upper limit value, the water dispersibility of the polymer (A) is more excellent.

[0142] The Mw of the polymer (A) is preferably 8,000 to 600,000, more preferably 16,000 to 400,000, and still more preferably 32,000 to 350,000. If the Mw of the polymer (A) is above the above lower limit value, the water repellency of the article treated with the present composition is more excellent. If the Mw of the polymer (A) is below the above upper limit value, the water dispersibility of the polymer (A) is more excellent.

[0143] (medium)

[0144] Examples of the medium include water, alcohol, diol, diol 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 preferably one or more media selected from the group consisting of water, alcohol, diol, diol ether, and diol ester.

[0145] 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.

[0146] Examples of the diol or diol 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, hexanediol, etc.

[0147] 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.

[0148] Examples of the hydrocarbon include aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, etc.

[0149] Examples of the aliphatic hydrocarbon include 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.

[0150] Examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc.

[0151] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc.

[0152] Examples of the ketone include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, etc.

[0153] Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, methyl lactate, ethyl lactate, pentyl lactate, etc.

[0154] Examples of the ether include diisopropyl ether, dioxane, tetrahydrofuran, etc.

[0155] Examples of the nitrogen compound include pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0156] Examples of the sulfur compound include dimethyl sulfoxide and sulfolane.

[0157] Examples of the inorganic solvent include liquid carbon dioxide.

[0158] Examples of the organic acid include acetic acid, propionic acid, malic acid, lactic acid, and the like.

[0159] The medium can be used alone 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 the combined media, it is easy to control the solubility and dispersibility of the polymer, and it is easy to control the penetrability, wettability, solvent drying rate, etc. with respect to the article during processing.

[0160] 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 still more preferably 3 to 25 parts by mass with respect to 100 parts by mass of water.

[0161] (Surfactant)

[0162] Examples of the surfactant include hydrocarbon surfactants. Examples of the hydrocarbon surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, or amphoteric surfactants.

[0163] From the viewpoint of dispersion stability, the surfactant is preferably a combination of a nonionic surfactant and a cationic surfactant or an amphoteric surfactant, or a single anionic surfactant, and preferably a combination of a nonionic surfactant and a cationic surfactant.

[0164] The mass ratio of the nonionic surfactant to the cationic surfactant is preferably 97 / 3 to 40 / 60.

[0165] In a specific combination of a nonionic surfactant and a cationic surfactant, the total amount with respect to the polymer (A) (100% by mass) can be 5% by mass or less, and thus, the adverse effect on the water repellency of the article can be reduced.

[0166] Examples of the nonionic surfactant preferably include one or more selected from the group consisting of surfactant s 1 ~s 6 constituting the group.

[0167] Surfactant s 1 :

[0168] Surfactant s 1It is a polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether or polyoxyalkylene monopolyenyl ether.

[0169] As surfactant s 1 , preferably a polyoxyalkylene monoalkyl ether or polyoxyalkylene monoalkenyl ether. Surfactant s 1 can be used alone, and two or more kinds can be used in combination.

[0170] As the alkyl, alkenyl or polyenyl group (hereinafter, the alkyl, alkenyl and polyenyl groups are collectively referred to as R s group), it is preferably a group having 4 to 26 carbon atoms. R s group can be straight-chain or branched-chain. As the branched-chain R s group, it is preferably a secondary alkyl, secondary alkenyl or secondary polyenyl group.

[0171] As specific examples of the R s group, octyl, dodecyl, tetradecyl, hexadecyl, stearyl (octadecyl), behenyl (docosyl), oleyl (9-octadecenyl), etc. can be cited.

[0172] As the polyoxyalkylene (hereinafter referred to as POA) chain, it is preferably any one or both of a polyoxyethylene (hereinafter referred to as POE) chain and a polyoxypropylene (hereinafter referred to as POP) chain connected by two or more. The POA chain can be a chain containing one kind of POA chain or a chain containing two or more kinds of POA chains. In the case of containing two or more kinds of POA chains, each POA chain is preferably connected in a block shape.

[0173] As surfactant s 1 , more preferably compound (s 11 ).

[0174] R 10 O[CH2CH(CH3)O] s -(CH2CH2O) r H…(s 11 ).

[0175] 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.

[0176] When r is 5 or more, it is soluble in water and uniformly dissolved in the aqueous medium, so the water repellent composition has good permeability to the article. When r is 50 or less, the hydrophilicity can be inhibited and the water repellency is good.

[0177] When s is 20 or less, it is soluble in water and uniformly dissolved in the aqueous medium, so the water repellent composition has good permeability to the article.

[0178] When r and s are 2 or more, the POE chain and the POP chain are connected in a block form.

[0179] As R 10 , it is preferably a straight chain or a branched chain.

[0180] r is preferably an integer from 10 to 30.

[0181] s is preferably an integer from 0 to 10.

[0182] As the compound (s 11 ), the following compounds can be cited. Among them, the POE chain and the POP chain are connected in a block form.

[0183] C 18 H 37 O[CH2CH(CH3)O]2-(CH2CH2O) 30 H,

[0184] C 18 H 35 O-(CH2CH2O) 30 H,

[0185] C 16 H 33 O[CH2CH(CH3)O]5-(CH2CH2O) 20 H,

[0186] C 12 H 25 O[CH2CH(CH3)O]2-(CH2CH2O) 15 H,

[0187] (C8H 17 )(C6H 13 )CHO-(CH2CH2O) 15 H,

[0188] C 10 H 21 O[CH2CH(CH3)O]2-(CH2CH2O) 15 H.

[0189] Surfactant s 2 :

[0190] Surfactant s 2 is a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in the molecule.

[0191] As surfactant s 2 , it is preferably a compound having one carbon-carbon triple bond and one or two hydroxyl groups in the molecule.

[0192] Surfactant s 2 It may have a POA chain in the molecule. Examples of the POA chain include a POE chain, a POP chain, a chain in which a POE chain and a POP chain are connected randomly, or a chain in which a POE chain and a POP chain are connected in a block form.

[0193] As the surfactant s 2 , it is preferably the compound (s 21 ) to (s 24 ).

[0194] HO-C(R 11 )(R 12 )-C≡C-C(R 13 )(R 14 )-OH…(s 21 ),

[0195] HO-(A 1 O) u -C(R 11 )(R 12 )-C≡C-C(R 13 )(R 14 )-(OA 2 ) v -OH…(s 22 ),

[0196] 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 are each 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, it is preferably a POE chain, a POP chain, or a chain containing a POE chain and a POP chain. The number of repeating units of the POA chain is preferably 1 to 50.

[0203] R 11 ~R 16 Are each a hydrogen atom or an alkyl group.

[0204] As the alkyl group, it is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. 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 )), it is preferably the compound(s 25 ).

[0206]

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

[0208] The compound(s 25 ) can be used alone as 1 kind, or 2 or more kinds can be used in combination.

[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 consecutive oxyalkylene groups having 3 or more carbon atoms are connected to a POA chain and a POE chain, and both ends are hydroxyl groups.

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

[0213] As surfactant s 3 , it is preferably the compound(s 31 ) or the 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 the surfactant s 3 , the following compounds can be listed.

[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] The surfactant s 4 :

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

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

[0230] (R17 )(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 ) may be used alone or in combination of two or more.

[0234] As compound (s 41 ), from the viewpoint of the dispersion stability of the polymer, compound (s 42 ) is preferred.

[0235] (R 20 )(CH3)2N(→O)···(s 42 )。

[0236] R 20 is an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, a phenyl group bonded to an alkyl group having 6 to 22 carbon atoms, or a phenyl group bonded to 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 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 a substituted phenyl group, it is preferably a phenyl group substituted with a monovalent hydrocarbon group, more preferably a phenyl group substituted with an alkyl group, an alkenyl group or a styryl group.

[0245] As surfactant s 5 , it is preferably 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.

[0246] As the condensate of polyoxyethylene mono(substituted phenyl) ether or polyoxyethylene mono(substituted phenyl) ether, there may be mentioned the 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.

[0247] Surfactant s 6 :

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

[0249] The polyhydric alcohol means glycerin, sorbitan, sorbitol, polyglycerol, polyethylene glycol, polyoxyethylene glycerol ether, polyoxyethylene sorbitan ether or polyoxyethylene sorbitol ether.

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

[0251] Surfactant s 7 :

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

[0253] Surfactant s 7 is a substituted ammonium salt.

[0254] As surfactant s 7, preferably an ammonium salt in which one or more hydrogen atoms bonded to a nitrogen atom are substituted with an alkyl group, an alkenyl group, or a POA chain having a hydroxyl group at the end, more preferably a compound (s 71 ).

[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 having a hydroxyl group at the end. The four Rs 21 are optionally the same or different, provided that the four Rs 21 are not simultaneously hydrogen atoms.

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

[0258] R 21 is an alkyl group other than a long-chain alkyl group, as R 21 , preferably methyl or ethyl.

[0259] R 21 is a POA chain having a hydroxyl group at the end, as the POA chain, preferably a POE chain.

[0260] X - is a counterion.

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

[0262] As the compound (s 71 ), examples include stearyl trimethyl ammonium chloride, stearyl dimethyl monoethyl ammonium ethyl sulfate, mono(stearyl)monomethyl di(polyethylene glycol) ammonium chloride, monofluorohexyl trimethyl ammonium chloride, di(tallow alkyl)dimethyl ammonium chloride, dimethyl mono coconut amine acetate, and the like.

[0263] Surfactant s 8 :

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

[0265] Surfactant s 8 is alanine-based, imidazolium betaine-based, amide betaine-based, or acetic acid betaine.

[0266] As surfactant s 8The hydrophobic group it has is preferably a long-chain alkyl group having 6 to 22 carbon atoms or a long-chain alkenyl group having 6 to 22 carbon atoms.

[0267] As surfactant s 8 , examples thereof include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolium betaine, lauryl dimethylaminoacetic acid betaine, fatty acid amide propyl dimethylaminoacetic acid betaine, and the like.

[0268] Surfactant s 9 :

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

[0270] Surfactant s 9 is a polymer surfactant composed of a block copolymer, random copolymer, or hydrophobic modification of a hydrophilic copolymer 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, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, and the like.

[0272] As surfactant s 9 Commercially available products thereof include MP polymers (product numbers: MP-103, MP-203) of Kuraray Co., Ltd., SMA resin of ELF ATOCHEM Co., Ltd., METOLOSE of Shin-Etsu Chemical Co., Ltd., EPOMIN RP of Nippon Shokubai Co., Ltd., and the like.

[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 resulting emulsion, it is preferably a combination of surfactant s 1 and surfactant s 2 and surfactant s 7 ; or a combination of surfactant s 1 and surfactant s 3 and surfactant s 7 ; or a combination of surfactant s 1 and surfactant s 2 and surfactant s 3 and surfactant s7 in combination, more preferably surfactant s 7 is the above combination of compound (s 71 ). The total amount of the surfactant is preferably 1 to 10 parts by mass, more preferably 1 to 7 parts by mass, relative to 100 parts by mass of the polymer.

[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. Examples of the molecular weight regulator include mercaptoethanol, mercaptopropionic acid, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, stearyl mercaptan, and α-methylstyrene dimer (CH2=C(Ph)CH2C(CH3)2Ph, where Ph is a phenyl group), and n-dodecyl mercaptan, tert-dodecyl mercaptan, and stearyl mercaptan are particularly preferred.

[0276] (Polymerization initiator)

[0277] Examples of the polymerization initiator include thermal polymerization initiators, photopolymerization initiators, radiation polymerization initiators, radical polymerization initiators, and ionic polymerization initiators, and radical polymerization initiators are preferred. As the radical polymerization initiator, for example, depending on the polymerization temperature, azo-based polymerization initiators, peroxide-based polymerization initiators, and redox initiators can be used. As the radical polymerization initiator, azo-based compounds are preferred, and salts of azo-based compounds are more preferred. Examples of the initiator include acetate of 2,2’-azobis[2-(2-imidazolin-2-yl)propane] (manufactured by Wako Pure Chemical Industries, Ltd., VA-061) and 2,2’-azobis(2-amidinopropane) (manufactured by Nippon Kayaku Co., Ltd., NC-32). The polymerization temperature is preferably 30 to 80°C.

[0278] (Other components)

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

[0280] As other components, crosslinking agents, penetrants, defoamers, water absorbents, antistatic agents, antistatic polymers, wrinkle preventers, handle modifiers, film-forming aids, water-soluble polymers (such as polyacrylamide and polyvinyl alcohol), thermosetting agents (such as melamine resin, urethane resin, compounds containing a triazine ring, and isocyanate-based compounds), epoxy curing agents (such as isophthalic dihydrazide, adipic dihydrazide, sebacic dihydrazide, dodecanedioic dihydrazide, 1,6-hexamethylenebis(N,N-dimethylaminourea), 1,1,1’,1,’-tetramethyl-4,4’-(methylenediphenylene)diaminourea, and spirodiol), thermosetting catalysts, crosslinking catalysts, synthetic resins, fiber stabilizers, inorganic fine particles, etc. can be cited.

[0281] The water repellent composition of the present embodiment may contain, as needed, polymers capable of exhibiting water repellency, commercially available water repellents, water repellent compounds without fluorine atoms, etc., in addition to the polymer (A) of the present embodiment. As the water repellent compounds without fluorine atoms, paraffin-based compounds, aliphatic amide-based compounds, alkylethyleneurea compounds, silicon-based compounds, 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, isocyanate-based crosslinking agents, hydroxymethyl-based crosslinking agents, carbodiimide-based crosslinking agents, and oxazoline-based crosslinking agents 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, aromatic-capped isocyanate-based crosslinking agents, aliphatic-capped isocyanate-based crosslinking agents, aromatic non-capped isocyanate-based crosslinking agents, and aliphatic non-capped isocyanate-based crosslinking agents 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-triazone, 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, etc.

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

[0289] As other crosslinking agents, for example, divinyl sulfone, polyamide and its cationic derivatives, polyamine and its cationic derivatives, epoxy derivatives such as diglycidyl glycerol, halogenated derivatives such as (epoxy-2,3-propyl) trimethylammonium chloride and N-methyl-N-(epoxy-2,3-propyl) morpholinium chloride, pyridinium salt of chloromethyl ether of ethylene glycol, polyamine-polyamide-epichlorohydrin resin, polyvinyl alcohol or its derivatives, polyacrylamide or its derivatives, and glyoxal resin-based anti-wrinkle agents can be cited.

[0290] When this composition contains a hydroxymethyl-based crosslinking agent or a glyoxal resin-based anti-wrinkle agent, as an additive, a catalyst is preferably contained. As preferred catalysts, for example, inorganic amine salts and organic amine salts can be cited. As inorganic amine salts, for example, ammonium chloride can be cited. As organic amine salts, for example, amino alcohol hydrochloride and semicarbazide hydrochloride can be cited. As amino alcohol hydrochloride, for example, monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanol hydrochloride, and 2-amino-2-methylpropanol hydrochloride can be cited.

[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 just after manufacturing this composition.

[0294] When this composition is used for treating an article, the solid content concentration of this composition is preferably 0.03 to 1.2% by mass, more preferably 0.05 to 1.0% by mass, and further preferably 0.08 to 0.9% by mass.

[0295] It should be noted that the solid content concentration refers to the total content of the polymer (A) and the surfactant in this composition.

[0296] The ratio of the polymer (A) to the total mass of this composition is preferably 0.03 to 60% by mass, more preferably 0.05 to 50% by mass, and further preferably 0.08 to 45% by mass.

[0297] When this composition contains a surfactant, the content of the surfactant in this composition is preferably 1 to 10 parts by mass, more preferably 1 to 8 parts by mass, and further preferably 2 to 7 parts by mass with respect to 100 parts by mass of the polymer (A).

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

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

[0300] The content of fluorine atoms relative to the total mass of the composition 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 composition can be measured by combustion ion chromatography or the like.

[0301] "Method for Producing Non-Fluorine Polymer"

[0302] The method for producing a non-fluorine polymer according to this embodiment is a production method in which a mixture containing a monomer component containing monomer (a), monomer (b), and monomer (c) is polymerized in the presence of a surfactant and a polymerization initiator. In addition, a water repellent composition is also produced. The proportion of monomer (a) is 73 to 95% by mass, the proportion of monomer (b) is 1 to 12% by mass, and the proportion of monomer (c) is 0.5 to 15% by mass relative to the total mass of all the monomers constituting the non-fluorine polymer.

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

[0304] Monomer (a), monomer (b), monomer (c), monomer (d), and monomer (e) can each be a monomer produced by a known production method. For 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 80% by mass or more, more preferably 80 to 99% by mass, and still more preferably 82 to 98% by mass relative to the total mass of the monomers constituting the non-fluorine polymer. If 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 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more relative to the total mass of the monomers constituting the non-fluorine polymer.

[0307] With respect to the total mass of the monomers constituting the non-fluoropolymer, the proportion of monomer (a) contained in the mixture is 73 to 95% by mass, preferably 74 to 92% by mass, more preferably 75 to 90% by mass. With respect to the total mass of monomer (a), monomer (b) and monomer (c) contained in the mixture, the proportion of monomer (a) is preferably 73 to 95% by mass, more preferably 75 to 95% by mass, further preferably 78 to 94% by mass. If the proportion of monomer (a) is above the above lower limit value, the water repellency of the article treated with this composition is more excellent. If the proportion of monomer (a) is below 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] With respect to the total mass of the monomers constituting the non-fluoropolymer, the proportion of monomer (b) contained in the mixture is 1 to 12% by mass, preferably 2 to 11% by mass, more preferably 3 to 10% by mass. With respect to the total mass of monomer (a), monomer (b) and monomer (c) contained in the mixture, the proportion of monomer (b) is preferably 1 to 12% by mass, more preferably 2 to 11% by mass, further preferably 3 to 10% by mass. If the proportion of monomer (b) is above the above lower limit value, the water repellency of the article treated with this composition is more excellent. If the proportion of monomer (b) is below 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] With respect to the total mass of the monomers constituting the non-fluoropolymer, the proportion of monomer (c) contained in the mixture is 0.5 to 15% by mass, preferably 0.8 to 14% by mass, more preferably 1 to 13% by mass. With respect to the total mass of monomer (a), monomer (b) and monomer (c) contained in the mixture, the proportion of monomer (c) is preferably 1 to 15% by mass, more preferably 1 to 14% by mass, further preferably 1 to 10% by mass. If the proportion of monomer (c) is above the above lower limit value, the water repellency of the article treated with this composition is more excellent. If the proportion of monomer (c) is below the above upper limit value, monomer (a) and monomer (b) can be sufficiently contained, 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 70% by mass or more, more preferably 75 - 98% by mass, and still more preferably 80 - 97% by mass, relative to the total mass of the monomers constituting the non-fluoropolymer. If 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. If 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 4 - 30% by mass, more preferably 5 - 25% by mass, and still more preferably 6 - 22% by mass, relative to the total mass of the monomers constituting the non-fluoropolymer. If 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. If 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 - 95% by mass, more preferably 55 - 90% by mass, and still more preferably 60 - 90% by mass, relative to the total mass of the monomers constituting the non-fluoropolymer. If 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. If 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 1.5 - 25, more preferably 2.0 - 24, and still more preferably 3.0 - 23. If 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. If the mass ratio of monomer (a) / monomer (b) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[0314] The mass ratio of monomer (b) / monomer (c) contained in the mixture is preferably 0.6 - 15, more preferably 0.7 - 13, and still more preferably 0.8 - 12. If 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. If the mass ratio of monomer (b) / monomer (c) is at most the above upper limit value, the polymerization of the monomer components is easy during the production of polymer (A).

[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 0.010 to 0.17. If the mass ratio of monomer (c) / monomer (a) is at or above the lower limit value, the water repellency of the article treated with this composition is more excellent. If the mass ratio of monomer (c) / monomer (a) is at or below the upper limit value, the polymerization of the monomer components is facilitated in the production of polymer (A).

[0316] The mass ratio of {monomer (a) + monomer (b)} / monomer (c) contained in the mixture is preferably from 1.0 to 120, more preferably from 1.5 to 110, and still more preferably from 2.0 to 100. If the mass ratio of {monomer (a) + monomer (b)} / monomer (c) is at or above the lower limit value, the water repellency of the article treated with this composition is more excellent. If the mass ratio of {monomer (a) + monomer (b)} / monomer (c) is at or below the upper limit value, the polymerization of the monomer components is facilitated in the production of polymer (A).

[0317] When the mixture contains monomer (d), the proportion of monomer (d) relative to the total mass of the monomer components 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) relative to the total mass of the monomer components 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) 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 weights (Mn, Mw) of polymer (A) can be obtained.

[0321] In the emulsion polymerization method, for example, the above-mentioned monomer component is polymerized in an emulsion containing a medium, a monomer component, 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 mentioned above.

[0323] Relative to 100 parts by mass of all the monomers constituting the non-fluoropolymer, the proportion of the above-mentioned 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 the medium, the monomer component, and, if necessary, the surfactant, dispersing them using a homogenizer, a high-pressure emulsifier, etc., and then adding the polymerization initiator. It should be noted that when the monomer component is a gas, it can be added to the reaction system after the above-mentioned 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 above 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 relative to 100 parts by mass of the monomer component. When the content of the surfactant is at least the above lower limit value, the dispersion stability of the emulsion is excellent. When the content of the surfactant is at most the above 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 relative to 100 parts by mass of the monomer component. When the content of the polymerization initiator is at least the above 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 above upper limit value, a polymer having a molecular weight in the desired range is easily obtained.

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

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

[0330] In the dispersion liquid, the average particle diameter of the emulsified particles of polymer (A) is preferably 10 to 1000 nm, more preferably 30 to 600 nm, and still more preferably 50 to 300 nm. When the average particle diameter is below the aforementioned upper limit value, the water repellency of the article treated with the emulsified particles of polymer (A) and the dispersibility of the emulsified particles of polymer (A) are more excellent. When the average particle diameter is above the aforementioned lower limit value, the emulsified particles of polymer (A) are more stable against mechanical shear force.

[0331] The average particle diameter of the emulsified particles of polymer (A) is calculated as follows: For a sample obtained by diluting the dispersion liquid of polymer (A) with water to a solid content concentration of 1% by mass, an autocorrelation function is obtained by dynamic light scattering method, and the average particle diameter is calculated by analyzing this function using the cumulant method.

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

[0333] <Treatment method of water repellent composition>

[0334] The treatment method of this embodiment is a treatment method using this composition. Any method that can attach this composition to the article to be treated can be used. For example, when this composition contains a liquid medium, methods such as coating, impregnation, dipping, spraying, brushing, filling, sizing, and rolling can be cited. After treating the article with this dispersion liquid by a known method, it is then dried.

[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, more preferably 0.1 to 3 g, and still more preferably 0.1 to 1 g relative to 100 g of the fiber fabric.

[0336] The amount of polymer (A) in the water repellent composition attached to the article to be treated is not particularly limited. For example, in the case of a fiber fabric, it is preferably 0.01 to 5 g, more preferably 0.02 to 3 g, and still more preferably 0.03 to 1 g relative to 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 aforementioned crosslinking agent for curing.

[0338] <Article>

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

[0340] Examples of the article to be treated with the present composition include fibers, fibrous fabrics (woven fabrics, knitted fabrics, non-woven fabrics, flocked fabrics, etc.), fiber products having a fibrous fabric (clothing materials such as ski suits, raincoats, outerwear, 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, fibrous fabrics, and fiber products having a fibrous fabric are preferred. The type of fiber is not particularly limited, and examples include natural fibers such as cotton, wool, silk, or cellulose, chemical fibers such as polyester, polyamide, acrylic, aramid, rayon, or tencel, and fibers obtained by using a plurality of these fibers. Examples of the fiber when the fiber substrate is a non-woven fabric include polyethylene, polypropylene, polyolefin, polyethylene terephthalate, polytetrafluoroethylene, glass, and rayon.

[0342] The thickness of the fibrous fabric is not particularly limited and is 10 μm to 5 cm.

[0343] (Mechanism of action)

[0344] Regarding the present composition described above, since the polymer (A) has the unit (a), the unit (b), and the unit (c), the water repellency and durability of the article treated with the present composition are excellent. In particular, even when the content of the non-fluoropolymer in the water repellent composition is low, good water repellency and durability are exhibited. As the reason, the following mechanism can be considered. It is considered that by including the unit (b) in the polymer (A), the adhesiveness to the article to be treated is improved, and thus the durability is improved. Furthermore, it is considered that a dense water repellent film is easily formed on the surface of the article, and the water repellency is also improved. It is considered that by making the proportion of the unit (b) 12% by mass or less, the water repellent film is less likely to become hydrophilic, and the water repellency is improved. It is considered that by including the unit (c) in the polymer (A), the water repellent film has improved slipperiness, and the water repellency is improved. In particular, it is considered that by making the molecular weight of the monomer (c) 1000 or more, the unit (c) is easily exposed on the surface of the water repellent film, and the water repellency is improved. In addition, it is considered that by making the molecular weight of the monomer (c) 3600 or less, the viscosity of the polysiloxane portion of the unit (c) that exhibits slipperiness due to exposure on the water repellent film surface does not become too high. As a result, it is considered that the viscosity of the polymer (A) does not become too high, the slipperiness of the water repellent film is improved, and the water repellency is improved.

[0345] Example

[0346] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. Examples 1 to 13 are examples, and Examples 14 to 41 are comparative examples.

[0347] <Ratio of monomer units>

[0348] The composition of the polymer (the ratio of each monomer unit to all the units constituting the polymer) is calculated based on the charged amount of the monomer components.

[0349] <Water repellent treatment of fabric: low concentration>

[0350] The emulsion obtained in the examples described below was diluted with distilled water, and the solid content concentration was adjusted to 0.2% by mass. Then, blocked isocyanate (MEIKANATE TP-10 manufactured by Meisei Chemical Industry Co., Ltd.) as a crosslinking agent was added as a co-auxiliary agent at a concentration of 1.5% by mass to prepare a water repellent composition. The dyed nylon fabric was immersed in this water repellent composition and wrung so that the content of the water repellent composition relative to the total mass of the water repellent composition and the dyed nylon fabric was 60% by mass. After drying it at 110°C for 90 seconds, it was further heat-treated at 170°C for 60 seconds to obtain a test fabric (low concentration).

[0351] <Water repellent treatment of fabric: high concentration>

[0352] The emulsion obtained in the examples described below was diluted with distilled water, and the solid content concentration was adjusted to 1.5% by mass. Then, blocked isocyanate (MEIKANATE TP-10 manufactured by Meisei Chemical Industry Co., Ltd.) as a crosslinking agent was added as a co-auxiliary agent at a concentration of 1.5% by mass to prepare a water repellent composition. The dyed nylon fabric was immersed in this water repellent composition and wrung so that the content of the water repellent composition relative to the total mass of the water repellent composition and the dyed nylon fabric was 60% by mass. After drying it at 110°C for 90 seconds, it was further heat-treated at 170°C for 60 seconds to obtain a test fabric (high concentration).

[0353] <Water repellency evaluation (initial)>

[0354] For the test fabric (low concentration) and the test fabric (high concentration), the water repellency was evaluated according to the spray test of JIS L1092-2009. The water repellency is represented by a 5-level scale from 1 to 5. The larger the score, the better the water repellency. When the grade is marked with +(-), it means that compared with the standard sample of the foregoing grade, various properties are slightly better (worse).

[0355] <Water repellency evaluation (after washing)>

[0356] For the test cloth (low concentration) and the test cloth (high concentration), they were repeatedly washed 20 times according to the washing method in Appendix 103 of JIS L0217. After washing, they were air-dried overnight in a room at 25°C and 60% humidity, and then the aforementioned water repellency was evaluated.

[0357] <Comprehensive Evaluation>

[0358] Regarding the 5-level rating from 1 to 5, +0.2 was added (e.g., 3+ = 3.2), and -0.2 was subtracted (e.g., 3- = 2.8). The sum of the water repellency evaluation (initial) and the water repellency evaluation (after washing) was used as the comprehensive evaluation.

[0359] The compound names described in this specification are as follows.

[0360] Monomer (a):

[0361] StA: Stearyl acrylate

[0362] BeA: Behenyl acrylate

[0363] Monomer (b):

[0364] VdCl: Vinylidene chloride

[0365] VCM: Vinyl chloride

[0366] Monomer (c):

[0367] Silicone monomer 1: Single-terminal methacryloyl-modified silicone (number average molecular weight: 2300, manufactured by Shin-Etsu Chemical Co., Ltd., X-22-174BX)

[0368] Silicone monomer 2: Double-terminal methacryloyl-modified silicone (number average molecular weight: 2370, manufactured by Shin-Etsu Chemical Co., Ltd., X-22-164C)

[0369] Silicone monomer 3: Double-terminal methacryloyl-modified silicone (number average molecular weight: 3200): It was synthesized by the method described in JP-A-59-78263.

[0370] Monomer (c’):

[0371] Silicone monomer 4: Single-terminal methacryloyl-modified silicone (number average molecular weight: 900, manufactured by Shin-Etsu Chemical Co., Ltd., X-22-174ASX)

[0372] Silicone monomer 5: Single-terminal methacryloyl-modified silicone (number average molecular weight: 4600, manufactured by Shin-Etsu Chemical Co., Ltd., KF-2012)

[0373] Silicone monomer 6: Single-terminal methacryloyl-modified silicone (number-average molecular weight: 12,000, manufactured by Shin-Etsu Chemical Co., Ltd., X-22-2426)

[0374] Silicone monomer 7: Two-terminal methacryloyl-modified silicone (number-average molecular weight: 3,900, manufactured by Shin-Etsu Chemical Co., Ltd., X-22-164E)

[0375] Monomer (d):

[0376] MOI-BP: 3,5-Dimethylpyrazole adduct of isocyanatoethyl acrylate

[0377] Monomer (e):

[0378] DMAA: Dimethylacrylamide

[0379] NMAM: N-Hydroxymethylacrylamide

[0380] Surfactant:

[0381] E420: Polyoxyethylene oleyl ether (EMULGEN (Kao Corporation, trade name) 420, about 13 moles of ethylene oxide adduct)

[0382] P204: 10 mass% aqueous solution of ethylene oxide-propylene oxide polymer (manufactured by NOF Corporation, trade name, PRONON 204, ethylene oxide proportion is 40 mass%)

[0383] AQ-18-63: Solution of 63% stearyl trimethyl ammonium chloride, 32% isopropyl alcohol, and 5% water (manufactured by LIONSPECIALTY CHEMICALS Co., Ltd.)

[0384] SmOA: Sorbitan monooleate

[0385] PELE: Polyoxyethylene lauryl ether

[0386] PEtDE: Polyoxyethylene tridecyl ether

[0387] dODACl: Dioctadecyl ammonium chloride

[0388] Molecular weight regulator:

[0389] LSH: Lauryl mercaptan

[0390] StSH: Stearyl mercaptan

[0391] Polymerization initiator:

[0392] VA-061A: Acetate of 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (manufactured by Wako Pure Chemical Industries, Ltd., VA-061)

[0393] AMPD: 2,2'-Azobis(2-amidinopropane) (manufactured by Nippo Chemical Co., Ltd., NC-32)

[0394] Medium:

[0395] DPG: Dipropylene glycol

[0396] TPG: Tripropylene glycol

[0397] Water

[0398] (Example 1)

[0399] <Manufacture of polymer emulsion>

[0400] Put 29.8 g of StA, 58.7 g of BeA, 2.0 g of MOI-BP, 2 g of DMAA, 13.0 g of silicone monomer, 1.0 g of StSH, 2.5 g of E420, 0.5 g of P-204, 0.5 g of AQ-18-63, 30 g of DPG, and 155 g of water into a glass beaker. After heating at 60°C for 30 minutes, mix using a homogenizing stirrer (manufactured by Nippon Seiki Co., Ltd., Bio Stirrer) to obtain a mixed solution. While maintaining the above mixed solution at 60°C, use a high-pressure emulsifier (manufactured by APV Rannie Co., Ltd., MINILABO) to process it at 40 MPa to obtain an emulsion. Pour this emulsion into a stainless-steel reactor and cool it to 40°C or lower. Then, add 4.5 g of VdCl and 0.5 g of VA-061A. After purging the gas phase with nitrogen, carry out a polymerization reaction at 60°C for 15 hours with stirring to obtain a polymer emulsion. Using the obtained emulsion, conduct the above water repellency evaluation (initial) and water repellency evaluation (after washing). The results are shown in Table 1.

[0401] (Examples 2, 4, 6 to 17, 19, 21 to 24, 26 to 34, 36, 37)

[0402] Using the monomers (a) to (e), surfactant, molecular weight regulator, polymerization initiator, and medium shown in Tables 1 to 3, and changing to the feeding ratios shown in Tables 1 to 3, otherwise operating in the same manner as in Example 1, a polymer emulsion is obtained. It should be noted that the feeding ratios in Tables 1 to 3 are in parts by mass. Using the obtained emulsion, conduct the above water repellency evaluation (initial) and water repellency evaluation (after washing). The results are shown in Tables 1 to 3.

[0403] (Example 3)

[0404] Put 29.8 g of StA, 58.7 g of BeA, 2.0 g of MOI-BP, 2 g of DMAA, 13.0 g of silicone monomer, 1.0 g of StSH, 2.5 g of E420, 0.5 g of P-204, 0.5 g of AQ-18-63, 30 g of DPG, and 155 g of water into a glass beaker. After heating at 60 °C for 30 minutes, use a homogenizer (manufactured by Nippon Seiki Seisakusho, biological stirrer) to mix and obtain a mixed solution.

[0405] While maintaining the above-mentioned mixed solution at 60 °C, use a high-pressure emulsifier (manufactured by APV Rannie, MINILABO) to process it at 40 MPa to obtain an emulsion. Put this emulsion into a stainless-steel reactor and cool it to below 40 °C. Add 0.5 g of VA-061A, replace the gas phase with nitrogen, then introduce 9.6 g of VCM, and carry out a polymerization reaction at 60 °C for 15 hours while stirring to obtain an emulsion of the polymer. Use the obtained emulsion to conduct the above-mentioned water repellency evaluation (initial) and water repellency evaluation (after washing). The results are shown in Table 1.

[0406] (Examples 5, 18, 20, 25, 35, 38 - 41)

[0407] Use the monomers (a) - (e), surfactant, molecular weight regulator, polymerization initiator, and medium shown in Tables 1 - 3, and change to the feeding ratios shown in Tables 1 - 3. Otherwise, operate in the same manner as in Example 3 to obtain an emulsion of the polymer. Use the obtained emulsion to conduct the above-mentioned water repellency evaluation (initial) and water repellency evaluation (after washing). The results are shown in Tables 1 - 3.

[0408] [Table 1]

[0409]

[0410] [Table 2]

[0411]

[0412] [Table 3]

[0413]

[0414] Examples 1 to 13 using monomer (a), monomer (b) and monomer (c), and having a proportion of the structural unit based on monomer (b) relative to the total amount of the structural units of the non-fluoropolymer of 1 to 12% by mass, show good water repellency and durability even when the content of the non-fluoropolymer in the water repellent composition is low (low concentration). In Example 14 where monomer (b) is not used, and Examples 36 and 37 where monomer (b) and monomer (c) are not used, when the content of the non-fluoropolymer in the water repellent composition is low (low concentration), the water repellency and durability are low. In Example 40 where the proportion of the structural unit based on monomer (b) relative to the total amount of the structural units of the non-fluoropolymer exceeds 12% by mass and monomer (c) is not used, when the content of the non-fluoropolymer in the water repellent composition is low (low concentration), the water repellency and durability are low. In Examples 15 to 20, 30 to 32, 34, 39, 41 where monomer (b) is not used or the proportion of the structural unit based on monomer (b) relative to the total amount of the structural units of the non-fluoropolymer exceeds 12% by mass, when the content of the non-fluoropolymer in the water repellent composition is low (low concentration), the water repellency and durability are low. In Examples 21 to 29, 33, 35, 38 where monomer (c) is not used, when the content of the non-fluoropolymer in the water repellent composition is low (low concentration), the water repellency and durability are low.

Claims

1. A water repellent composition comprising a non-fluorinated polymer 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 (meth)acrylate monomer having a polysiloxane structure. The (meth)acrylate monomer having a polysiloxane structure has a molecular weight of 1,000 to 3,600. The proportion of the structural unit based on the vinyl halide monomer relative to the total amount of the structural units of the non-fluorinated polymer is 1 to 12% by mass.

2. The water repellent composition according to claim 1, wherein, The total proportion of the structural unit based on the (meth)acrylic acid long-chain alkyl ester monomer, the structural unit based on the vinyl halide monomer, and the structural unit based on the (meth)acrylate monomer having a polysiloxane structure relative to the total amount of the structural units of the non-fluorinated polymer is 80% by mass or more.

3. The water repellent composition according to claim 1, wherein, The vinyl halide monomer is vinyl chloride or vinylidene chloride.

4. The water repellent composition according to claim 1, wherein, The (meth)acrylate monomer having a polysiloxane structure is represented by the following formula (1) or formula (2). R 1 -(Si(R 2 )2O) m -Si(R 2 )2-R 3 OC(=O)CR 4 =CH2 (1) In the formula (1), R 1 represents a monovalent hydrocarbon group having 1 to 12 carbon atoms; R 2 represents H or CH3; R 3 represents a divalent hydrocarbon group having 1 to 6 carbon atoms; R 4 represents H, CH3 or a chlorine atom; m represents an integer of 8 to 55; a plurality of R 2 are optionally the same or different, CH2=CR 5 C(=O)OR 6 -(Si(R 7 )2O) n -Si(R 7 )2-R 6 OC(=O)CR 5 =CH2 (2) In the formula (2), R 5 represents H, CH3 or a chlorine atom; R 6 represents a divalent hydrocarbon group having 1 to 6 carbon atoms; R 7 represents H or CH3; n represents an integer from 8 to 55; multiple Rs 5 are optionally the same or different; multiple Rs 6 are optionally the same or different; multiple Rs 7 are optionally the same or different.

5. The water repellent composition according to claim 1, wherein, The (meth)acrylic acid long-chain alkyl ester monomer is represented by the following formula (3). R 9 -OC(=O)CR 8 =CH2 (3) In the formula (3), R 8 represents H, CH3 or a chlorine atom; R 9 represents an alkyl group having 12 to 30 carbon atoms.

6. The water repellent composition according to claim 5, 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 (3) 9 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 (3). 9 ​ 7. The water repellent composition according to claim 6, wherein Based on R in the formula (3) 9 The total proportion of the structural units of the long-chain alkyl (meth)acrylate monomer having 19 to 30 carbon atoms relative to the total amount of the structural units based on the long-chain alkyl (meth)acrylate monomer is 50 to 99% by mass.

8. The water repellent composition according to claim 1, wherein The non-fluorinated polymer further has a structural unit based on a crosslinkable monomer.

9. A method for manufacturing a non-fluorinated polymer, wherein, In the presence of a surfactant and a polymerization initiator, a mixture containing a (meth)acrylic acid long-chain alkyl ester monomer, a vinyl halide monomer, and a (meth)acrylate monomer having a polysiloxane structure is polymerized. Relative to the total mass of all the monomers constituting the non-fluorinated polymer, the proportion of the (meth)acrylic acid long-chain alkyl ester monomer is 73 to 95% by mass, the proportion of the vinyl halide monomer is 1 to 12% by mass, and the proportion of the (meth)acrylate monomer having a polysiloxane structure is 0.5 to 15% by mass.

10. A treatment method using the water repellent composition according to any one of claims 1 to 8.

11. An article obtained by treating with the water repellent composition according to any one of claims 1 to 8.

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