Water repellent composition

Abstract

To provide a polymer that can impart superior water repellency, skip resistance and chalk mark resistance to a fiber product.SOLUTION: Disclosed is a water repellent composition comprising a polymer (A), a polyether-modified polydimethylsiloxane (B), and an aqueous medium (C), wherein the polymer (A) includes a repeating unit that is derived from a monomer (a1) represented by the following formula: CH2=C(-R11)-C(=O)-R12. [In the formula, R11 represents a hydrogen atom or a methyl group, and R12 represents a hydrocarbon group having 9 to 40 carbon atoms].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a water repellent composition. [Background technology]

[0002] Development of non-fluorine-based water repellents is underway to impart water repellency to substrates (especially textiles). For example, it is known that treating fabric with a high concentration of a composition containing a blend of a non-fluorine-containing acrylic ester copolymer and a polyether-modified polydimethylsiloxane can provide excellent oil repellency. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2022 / 145147 [Patent Document 2] International Publication No. 2021 / 132172 [Patent Document 3] Japanese Patent Application Publication No. 2020-189980 Summary of the Invention [Problem to be solved by the invention]

[0004] The water repellency of the composition is insufficient for use as a water repellent. Furthermore, when conventional non-fluorine-based repellents are used in textile products, the slip resistance and chalk mark resistance are insufficient, which may reduce the reliability of the textile products.

[0005] An object of the present disclosure is to provide a water repellent composition that can impart good water repellency, slip resistance, and chalk mark resistance to textile products. [Means for solving the problem]

[0006] The present disclosure includes the following aspects: [Section 1] A polymer (A), Polyether-modified polydimethylsiloxane (B), and an aqueous medium (C), The polymer (A) has the following formula: CH2=C(-R 11 )-C(=O)-OR 12 [In the formula, R 11 is a hydrogen atom or a methyl group, R 12 is a hydrocarbon group having 9 to 40 carbon atoms. The water repellent composition is a polymer containing a repeating unit derived from a monomer (a1) represented by the following formula: [Section 2] In the above monomer (a1), R 12 Item 2. The water repellent composition according to Item 1, wherein is a hydrocarbon group having 10 to 30 carbon atoms. [Section 3] Item 3. The water repellent composition according to Item 2, wherein the polymer (A) contains a repeating unit derived from stearyl acrylate as the monomer (a1). [Section 4] Item 4. The water repellent composition according to any one of Items 1 to 3, wherein the polymer (A) is a copolymer containing a repeating unit derived from the monomer (a1) and a repeating unit derived from a monomer (a2) different from the monomer (a1). [Section 5] Item 5. The water repellent composition according to Item 4, wherein the polymer (A) contains a repeating unit derived from stearyl acrylate as the monomer (a1) and a repeating unit derived from a stearyl group-containing amide acrylate as the monomer (a2). [Section 6] Item 5. The water repellent composition according to Item 4, wherein the polymer (A) contains a repeating unit derived from stearyl acrylate as the monomer (a1) and a repeating unit derived from vinyl chloride as the monomer (a2). [Section 7] Item 5. The water repellent composition according to Item 4, wherein the polymer (A) contains, as the monomer (a1), a repeating unit derived from stearyl acrylate, and, as the monomer (a2), a repeating unit derived from a stearyl group-containing amide acrylate and a repeating unit derived from vinyl chloride. [Section 8] 8. The water repellent composition according to any one of items 1 to 7, comprising 0.10 to 30 parts by mass of the polyether-modified polydimethylsiloxane (B) per 100 parts by mass of the polymer (A). [Section 9] Item 9. The water repellent composition according to any one of items 1 to 8, wherein the polyether-modified polydimethylsiloxane (B) contains at least one structural unit based on ethylene oxide or propylene oxide. [Section 10] Item 10. The water repellent composition according to any one of items 1 to 9, further comprising a surfactant. [Section 11] Item 11. The water repellent composition according to Item 10, wherein the surfactant comprises a nonionic surfactant. [Section 12] Item 12. A method for producing the water repellent composition according to any one of Items 1 to 11, comprising the step of reacting the monomer (a1) in the aqueous medium (C) containing the monomer (a1) and the polyether-modified polydimethylsiloxane (B) to obtain the polymer (A). [Section 13] Item 12. A method for producing the water repellent composition according to any one of Items 4 to 11, comprising the step of reacting the monomer (a1) with the monomer (a2) in the aqueous medium (C) containing the monomer (a1), the monomer (a2), and the polyether-modified polydimethylsiloxane (B) to obtain the polymer (A). [Section 14] Item 12. A method for producing a textile product, comprising applying the water repellent composition according to any one of items 1 to 11 to a textile substrate. [Section 15] Before applying the water repellent composition to the fiber substrate, -SO3M 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. [Section 16] 12. A textile product to which the polymer (A) and the polyether-modified polydimethylsiloxane (B) in the water repellent composition according to any one of items 1 to 11 are attached. [Section 17] -SO3M 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 Item 17. The textile product according to Item 16, to which a compound having one or more functional groups selected from the group consisting of monovalent groups represented by the following formula: [Effects of the Invention]

[0007] The water repellent composition of the present disclosure can impart good water repellency, slip resistance, and chalk mark resistance to textile products. DETAILED DESCRIPTION OF THE INVENTION

[0008] <Terminology> As used herein, an "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. An "n-valent organic group" refers to an n-valent group containing carbon. Such organic groups are not particularly limited, but may be hydrocarbon groups or derivatives thereof. A hydrocarbon group derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the end or molecular chain of the hydrocarbon group.

[0009] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C 1-20 Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents.

[0010] The chemical structures described herein should be understood not to encompass chemical structures that would be recognized by those skilled in the art as chemically impossible or extremely unstable.

[0011] <Water repellent composition> The composition of the present disclosure will now be described.

[0012] The water repellent composition may further contain other components (such as silicone, wax, organic acid, surfactant, organic solvent, etc.).

[0013] [Polymer (A)] The polymer (A) preferably does not contain a fluorine atom.

[0014] (Monomer (a1)) The polymer (A) has the following formula: CH2=C(-RA1 )-C(=O)-OR A2 [In the formula, R A1 is a hydrogen atom or a methyl group, R A2 is a hydrocarbon group having 9 to 40 carbon atoms. The polymer (A) may further contain one or more other monomers (a2).

[0015] R A1 is a hydrogen atom or a methyl group.

[0016] R A2 is a hydrocarbon group having 9 to 40 carbon atoms. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. The -CH3 group has a lower surface free energy than the -CH2- group and is more likely to exhibit liquid repellency. For this reason, a structure with many branches and many -CH3 groups is preferred. On the other hand, long-chain alkyl groups of a certain length exhibit high liquid repellency due to their crystallinity.

[0017] R A2 may be linear or branched. A2 In another embodiment, R A2 is branched.

[0018] R A2 is more preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (i.e., an alkyl group). The hydrocarbon group has 9 to 40 carbon atoms. The lower limit of the number of carbon atoms in the hydrocarbon group may be 9, 10, 11, 12, 15, or 20. The upper limit of the number of carbon atoms in the hydrocarbon group may be 40, 35, 32, 30, 28, 26, 25, or 24. Examples of the number of carbon atoms in the hydrocarbon group include 9 to 35, 10 to 35, 10 to 30, and 15 to 25.

[0019] R A2It is preferable that the polymer does not have a reactive group or a hydrophilic group. Examples of reactive groups include epoxy groups, chloromethyl groups, bromomethyl groups, iodomethyl groups, isocyanate groups, and blocked isocyanate groups. Examples of hydrophilic groups include hydroxyl groups, polyalkylene oxide groups, amino groups, carboxylic acid groups, sulfonic acid groups, phosphate groups, alkali metal or alkaline earth metal bases of carboxylic acid, sulfonic acid, and phosphate, ammonium bases with chlorine, bromine, or iodine ions as counter anions, and other ionic groups. Here, the reactive group and the hydrophilic group may overlap with each other.

[0020] Preferred specific examples of the monomer (a1) include stearyl (meth)acrylate, isostearyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, icosyl (meth)acrylate, and behenyl (meth)acrylate.

[0021] In a preferred embodiment, the polymer (A) contains repeating units derived from stearyl acrylate as the monomer (a1).

[0022] The polymer (A) may be a copolymer containing repeating units derived from a monomer (a2) different from the monomer (a1). Examples of the monomer (a2) are described below.

[0023] (Monomer (a2)) The monomer (a2) may be a hydrophobic monomer (a21).

[0024] (Hydrophobic monomer (a21)) The hydrophobic monomer (a21) has one ethylenically unsaturated double bond and a hydrocarbon group having 2 to 40 carbon atoms.

[0025] The hydrophobic monomer (a21) may have at least one hydrocarbon group having 2 to 40 carbon atoms. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be linear or branched. The number of carbon atoms in the hydrocarbon group may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 11 or more, 12 or more, 14 or more, or 16 or more, preferably 6 or more. The number of carbon atoms in the hydrocarbon group may be 40 or less, 30 or less, 25 or less, 22 or less, or 20 or less, preferably 30 or less.

[0026] The hydrophobic monomer (a21) has the formula: CH2=C(-R 32 )-C(=O)-Y 31 -(R 31 ) k [In the formula, R 31 is a hydrocarbon group having 2 to 40 carbon atoms, R 32 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 31 represents a direct bond, a divalent to tetravalent hydrocarbon group having 1 carbon atom, and a divalent to tetravalent group consisting of at least one selected from -CH-, -O-, -C(=O)-, -S(=O)-, and -NR'- (R' represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms); k is an integer from 1 to 3. The monomer may be represented by the formula:

[0027] R 31is preferably a branched or linear (preferably long-chain linear) hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The -CH3 group has a lower surface free energy than -CH2- and is more likely to exhibit liquid repellency. For this reason, a structure with many branches and many -CH3 groups is preferred. On the other hand, long-chain alkyl groups of a certain length exhibit high liquid repellency due to their crystallinity. Therefore, R may be a branched hydrocarbon group (for example, a branched alkyl group), particularly a t-butyl group or an isopropyl group, a group with a multi-branched structure, or a long-chain hydrocarbon group (or a long-chain linear hydrocarbon group), for example, an alkyl group. 31 The number of carbon atoms in R may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 11 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and is preferably 10 or more. 31 may have 40 or fewer, 30 or fewer, 25 or fewer, 20 or fewer, 15 or fewer, or 12 or fewer carbon atoms.

[0028] k is 1, 2, or 3. Y 31 In the case where Y has a tetravalent hydrocarbon group having one carbon atom, k=3. 31 In the case where Y has a trivalent hydrocarbon group having one carbon atom, k=2. 31 does not have a trivalent or tetravalent hydrocarbon group having one carbon atom (for example, Y 31 has (for example, 1 to 6) divalent hydrocarbon groups (-CH2-) having one carbon atom, then k=1.

[0029] R 32 R may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. 32 Examples of R are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. 32 is preferably a hydrogen atom, a methyl group, or a chlorine atom. 32 More preferably, R is a methyl group. 32 When R is a methyl group, higher liquid repellency is obtained. 32 may be a hydrogen atom, particularly from the viewpoint of reactivity.

[0030] Y 31 is preferably a divalent group. Examples of the divalent to tetravalent hydrocarbon group having 1 carbon atom include -CH2-, -CH= having a branched structure, and -C≡ having a branched structure.

[0031] Y 31 -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-X'-, -Y'-X'-Y'- , -Y'-X'-Y'-C(=O)-, -Y'-X'-C(=O)-Y'-, -Y'-X'-Y'-C(=O)-Y'-, or -Y'-X'-Y'-X'- [In the formula, each Y' independently represents a direct bond, -O-, -NR'- (R' represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), or -S(=O)2-, X' is -(CH2) m -(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l - (each l is independently an integer of 0 to 5, and -C6H4- is a phenylene group). Y 31 is preferably not only a divalent hydrocarbon group.

[0032] Y 31 Specific examples are -O-, -NH-, -OC(=O)-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2)m -C(=O)-O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, NH-(CH2) m -NH-S(=O)2-, NH-(CH2) m -S(=O)2-NH--NH-(CH2) m -O-C(=O)-NH-, NH-(CH2) m [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​-OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -NH-C(=O)-NH- [In the formula, m is an integer of 1 to 5, particularly 2 or 4.] It is preferable that Y 31 is -O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, or -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, especially -O-(CH2) m It is more preferably -NH-C(=O)-.

[0034] The hydrophobic monomer (a21) preferably does not have a reactive group or a hydrophilic group. Examples of reactive groups include epoxy groups, chloromethyl groups, bromomethyl groups, iodomethyl groups, isocyanate groups, and blocked isocyanate groups. Examples of hydrophilic groups include hydroxyl groups, polyalkylene oxide groups, amino groups, carboxylic acid groups, sulfonic acid groups, phosphate groups, alkali metal or alkaline earth metal salts of carboxylic acid, sulfonic acid, and phosphate, ammonium salts with chlorine, bromine, or iodine ions as counter anions, and other ionic groups. Here, the reactive group and the hydrophilic group may overlap with each other.

[0035] The hydrophobic monomer (a21) may have a water solubility at 25°C of 10 g / L or less, 5 g / L or less, 3 g / L or less, 1 g / L or less, 0.5 g / L or less, or 0.1 g / L or less, preferably 3 g / L or less. The homopolymer of the hydrophobic monomer (a21) may have a water solubility at 25°C of 10 g / L or less, 5 g / L or less, 3 g / L or less, 1 g / L or less, 0.5 g / L or less, or 0.1 g / L or less, preferably 3 g / L or less.

[0036] Specific examples of the hydrophobic monomer (a21) are as follows: The compound of the following chemical formula is an acrylic compound having a hydrogen atom at the α-position, but may also be a methacrylic compound having a methyl group at the α-position or an α-chloroacrylic compound having a chlorine atom at the α-position. CH2=CHC(=O)OC 18 H 37 CH2=CHC(=O)OC n H 2n+1 CH2=CHC(=O)OC2H4OC(=O)NHC 18 H 37 CH2=CHC(=O)OC2H4NHC(=O)OC 18 H 37 CH2=CHC(=O)OC m H 2m NHC(=O)C n H 2n+1 CH2=CHC(=O)OC2H4OC(=O)NHC n H 2n+1 CH2=CHC(=O)OC2H4NHC(=O)OC n H 2n+1 CH2=CHC(=O)OC2H4NHC(=O)NHC n H 2n+1 CH2=CHC(=O)OC4H8OC(=O)NHC n H 2n+1 CH2=CHC(=O)NHC m H 2m OC(=O)NHC n H 2n+1 [ka] [ka] CH2=CHC(=O)OC m H 2m NHSO2C n H 2n+1 CH2=CHC(=O)OC m H 2m SO2NHC n H 2n+1 [In the above formula, n is a number from 3 to 40, and m is a number from 1 to 5.] [ka]

[0037] Preferred specific examples of the hydrophobic monomer (a21) include stearyl (meth)acrylate, butyl (meth)acrylate, t-butyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, icosyl α-chloroacrylate, behenyl α-chloroacrylate, stearamidoethyl (meth)acrylate, 2-stearamidoethyl acrylate, CH═CHC(═O)OCHNHSOC 18 H 37 These may be used alone or in combination of two or more.

[0038] From the viewpoint of the liquid repellency of the dispersion, the hydrophobic monomer (a21) may contain a hydrophobic monomer (a21) having an amide group, a urea group, or a urethane group. A combination of a hydrophobic monomer (a21) having an amide group, a urea group, or a urethane group with a hydrophobic monomer (a21) not having an amide group, a urea group, or a urethane group may also be used. Examples of the hydrophobic monomer (a21) having an amide group, a urea group, or a urethane group include a hydrophobic monomer (a21) having a CH═C(-R 32 )-C(=O)-O-(CH2) m -NH-C(=O)-R 31 , CH2=C(-R 32 )-C(=O)-O-(CH2) m -OC(=O)-NH-R 31 , CH2=C(-R 32)-C(=O)-O-(CH2) m -NH-C(=O)-OR 31 , and CH2=C(-R 32 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R 31 The hydrophobic monomer (a21) is CH2=C(-R 32 )-C(=O)-O-(CH2) m -NH-C(=O)-R 31 may include:

[0039] Preferred examples of the hydrophobic monomer (a21) having an amide group include compounds represented by the following formula (that is, stearyl group-containing amide acrylates). [ka]

[0040] Monomer (a2) may be a chloride monomer (a22).

[0041] (Chloride monomer (a22)) The polymer (A) may have a repeating unit derived from at least one chloride monomer (a22) selected from the group consisting of vinyl chloride and vinylidene chloride. The chloride monomer (a22) is preferably vinyl chloride.

[0042] The monomer (a2) may be a cyclic hydrocarbon group-containing monomer (a23).

[0043] (Cyclic hydrocarbon group-containing monomer (a23)) The polymer (A) may have a repeating unit derived from a cyclic hydrocarbon group-containing monomer (a23). The cyclic hydrocarbon group-containing monomer (a23) is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.

[0044] The cyclic hydrocarbon group-containing monomer (a23) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may, for example, have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0045] The cyclic hydrocarbon group may be aliphatic or aromatic, preferably aliphatic. The cyclic hydrocarbon group may be saturated or unsaturated, preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, preferably a bridged ring group. The cyclic hydrocarbon group may have a chain group (e.g., a linear or branched chain hydrocarbon group).

[0046] The cyclic hydrocarbon group may have 4 or more, 6 or more, or 8 or more carbon atoms, and may have 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less carbon atoms.

[0047] Specific examples of cyclic hydrocarbon groups include cyclohexyl, t-butylcyclohexyl, adamantyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, bornyl, isobornyl, norbornyl, dicyclopentanyl, dicyclopentenyl, benzyl, phenyl, naphthyl, 2-t-butylphenyl, residues obtained by removing one or more hydrogen atoms from these groups (e.g., cyclohexylene, adamantylene, phenylene, naphthylene, etc.), and groups that are substitution products thereof.

[0048] Specific examples of the cyclic hydrocarbon group-containing monomer (a23) include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and compounds in which these acrylates are substituted with acrylamide, etc. These may be used alone or in combination of two or more.

[0049] The monomer (a2) may be a crosslinkable monomer (a24).

[0050] (Crosslinkable monomer (a24)) The polymer (A) may have a repeating unit derived from a crosslinkable monomer (a24). The crosslinkable monomer (a24) is a monomer capable of imparting crosslinkability to the copolymer and may have at least two groups selected from the group consisting of reactive groups and olefinic carbon-carbon double bonds. The crosslinkable monomer (a24) may be a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group.

[0051] The crosslinkable monomer (a24) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0052] Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, a carbonyl group, an isocyanate group (blocked isocyanate group), and the like.

[0053] Specific examples of the crosslinkable monomer (a24) include diacetone (meth)acrylamide, N-methylol (meth)acrylamide, hydroxyethyl (meth)acrylamide, glycidyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and compounds in which these acrylates are substituted with acrylamide. These may be used alone or in combination of two or more. These may be used alone or in combination of two or more.

[0054] The monomer (a2) may be a monomer (a25) other than the above monomers (a21) to (a24).

[0055] (Other monomers (a25))

[0056] Specific examples of the other monomer (a25) include ethylene, halogenated olefin, vinyl acetate, acrylonitrile, alkoxypolyalkylene glycol (meth)acrylate, and vinyl alkyl ether. The other non-fluorine-containing monomer is not limited to these examples. These may be used alone or in combination of two or more.

[0057] In a preferred embodiment, the polymer (A) contains, as the monomer (a2), a repeating unit derived from a stearyl group-containing amide acrylate.

[0058] In another preferred embodiment, the polymer (A) contains, as the monomer (a2), a repeating unit derived from vinyl chloride.

[0059] (Polymer composition) The polymer (A) may be a homopolymer containing repeating units derived from one type of monomer (a1), or a copolymer containing repeating units derived from multiple types of monomers (a1). The polymer (A) may also be a copolymer containing repeating units derived from one or more types of monomers (a1) and repeating units derived from one or more types of monomers (a2). In a preferred embodiment, the polymer (A) is a homopolymer containing repeating units derived from one type of monomer (a1). In another preferred embodiment, the polymer (A) is a copolymer containing repeating units derived from one type of monomer (a1) and one type of monomer (a2).

[0060] In yet another preferred embodiment, the polymer (A) is a copolymer containing repeating units derived from one type of monomer (a1) and two types of monomers (a2). As an example of such an embodiment, the polymer (A) may contain repeating units derived from stearyl acrylate as the monomer (a1), and repeating units derived from a stearyl group-containing amide acrylate and vinyl chloride as the monomers (a2).

[0061] The amount of repeating units derived from monomer (a1) may be 15% by weight or more, 20% by weight or more, 25% by weight or more, 35% by weight or more, 45% by weight or more, 55% by weight or more, or 65% by weight or more, based on the entire polymer (A). The amount of repeating units derived from monomer (a1) may be 98% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less, based on the entire polymer (A).

[0062] When polymer (A) is a copolymer containing repeating units derived from monomer (a1) and repeating units derived from monomer (a2), monomer (a2) may be any one of the above monomers (a21) to (a24), or may contain two or more different monomers from the above monomers (a21) to (a24). For example, monomer (a2) may contain only one or two or more of the monomers contained in the above hydrophobic monomer (a21). Alternatively, monomer (a2) may contain one or two or more of the monomers contained in the above hydrophobic monomer (a21) and one or two or more of the monomers contained in the above chloride monomer (a22).

[0063] When the polymer (A) is a copolymer containing a repeating unit derived from the monomer (a1) and a repeating unit derived from the monomer (a2), the monomer (a2) is preferably a hydrophobic monomer (a21) or a chloride monomer (a22).

[0064] The proportion of the hydrophobic monomer (a21) having an amide group, urea group, or urethane group in the repeating units derived from the hydrophobic monomer (a21) may be 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, or 75% by weight or more. The proportion of the hydrophobic monomer (a1) having an amide group, urea group, or urethane group in the repeating units derived from the hydrophobic monomer (a21) may be 100% by weight or less, 90% by weight or less, 80% by weight or less, or 70% by weight or less.

[0065] The amount of repeating units derived from chloride monomer (a22) may be 3% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, or 35% by weight or more, based on the total weight of polymer (A). The amount of repeating units derived from chloride monomer (a2) may be 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less, based on the total weight of polymer (A), and is preferably 60% by weight or less.

[0066] The amount of repeating units derived from the cyclic hydrocarbon group-containing monomer (a23) may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, based on the entire polymer (A). The amount of repeating units derived from the cyclic hydrocarbon group-containing monomer (a23) may be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, or 5% by weight or less, based on the entire polymer (A).

[0067] The amount of the repeating units derived from the crosslinkable monomer (a24) may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, based on the entire polymer (A). The amount of the repeating units derived from the crosslinkable monomer (a24) may be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, or 5% by weight or less, based on the entire polymer (A).

[0068] The amount of repeating units derived from other monomers (a25) may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, based on the total weight of the polymer (A). The amount of repeating units derived from other monomers (a25) may be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less, based on the total weight of the polymer (A).

[0069] The amount of the repeating units derived from the chloride monomer (a22) may be 5 parts by weight or more, 10 parts by weight or more, 25 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the repeating units derived from the hydrophobic monomer (a21). The amount of the repeating units derived from the chloride monomer (a2) may be 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, or 25 parts by weight or less, per 100 parts by weight of the repeating units derived from the hydrophobic monomer (a21).

[0070] The amount of the repeating units derived from the cyclic hydrocarbon group-containing monomer (a23) may be 2.5 parts by weight or more, 5 parts by weight or more, 12.5 parts by weight or more, 25 parts by weight or more, 35 parts by weight or more, or 45 parts by weight or more, based on 100 parts by weight of the repeating units derived from the hydrophobic monomer (a21). The amount of the repeating units derived from the cyclic hydrocarbon group-containing monomer (a23) may be 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, based on 100 parts by weight of the repeating units derived from the hydrophobic monomer (a21).

[0071] The amount of the repeating units derived from the crosslinkable monomer (a24) may be 2.5 parts by weight or more, 5 parts by weight or more, 12.5 parts by weight or more, 25 parts by weight or more, 35 parts by weight or more, or 45 parts by weight or more, based on 100 parts by weight of the repeating units derived from the hydrophobic monomer (a21). The amount of the repeating units derived from the crosslinkable monomer (a24) may be 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, based on 100 parts by weight of the repeating units derived from the hydrophobic monomer (a21).

[0072] The amount of the repeating units derived from the other monomer (a25) may be 2.5 parts by weight or more, 5 parts by weight or more, 12.5 parts by weight or more, 25 parts by weight or more, 35 parts by weight or more, or 45 parts by weight or more, relative to 100 parts by weight of the repeating units derived from the hydrophobic monomer (a21). The amount of the repeating units derived from the other monomer (a25) may be 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 100 parts by weight of the repeating units derived from the hydrophobic monomer (a21).

[0073] The total amount of the repeating units derived from the hydrophobic monomer (a21) and the repeating units derived from the chloride monomer (a22) may be 50% by weight or more, 60% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more, based on the total amount of the polymer (A).

[0074] When polymer (A) is a copolymer containing repeating units derived from monomer (a1) and repeating units derived from monomer (a2), the amount of repeating units derived from monomer (a2) is not particularly limited and may be, for example, 0.5% by mass or more, 1% by mass or more, 3% by mass or more, or 4% by mass or more, relative to polymer (A). Also, the amount of repeating units derived from monomer (a2) may be, for example, 50% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 7.5% by mass or less, or 5% by mass or less, relative to polymer (A).

[0075] [Polyether-modified polydimethylsiloxane (B)] The polyether-modified polydimethylsiloxane (B) is represented by the following formula: TIFF0007791477000005.tif3778[In the formula, R 21 and R 22 is, each occurrence independently, —CH or —R 27 and R 23 and R 24 are each independently -CH3 or -R 27 and R 25 and R 26 are each independently a hydrogen atom or a monovalent organic group, R 27 -R 271 -R 272 -R 273 is a group represented by R 271 is a single bond or a divalent organic group, R 272 is a divalent polyether group, R 273 is a hydrogen atom or a monovalent organic group, p is an integer greater than or equal to 1. and at least one -R is present in one molecule of the polyether-modified polydimethylsiloxane (B). 27 Includes:

[0076] R 21 , and R 22 is, each occurrence independently, —CH or —R 27 is.

[0077] R 21 , and R 22 may all be methyl groups, and all R 21 , and R 22 At least one of them is -R 27 Preferably, all R appearing in one molecule may be 21 , and R 22 At least one of them is -R 27 is.

[0078] R 23 and R 24 are each independently -CH3 or -R 27 is.

[0079] R 23 and R 24 may be the same group or different groups. 23 and R 24 is a methyl group.

[0080] R 27 -R 271 -R 272 -R 273 It is a group represented by the following formula:

[0081] R 271 is a single bond or a divalent organic group.

[0082] The type of the divalent organic group is not particularly limited, but examples thereof include C1-6 Examples of the alkyl group include an alkyl group and an aryl group.

[0083] Above C 1-6 The alkyl group may be a straight chain or a branched chain. 1-6 The alkyl group may include a cyclic structure. 1-6 The alkyl group is linear. 1-6 The alkyl group is branched. 1-6 The alkyl group is C 3-6 It is a cyclic alkyl group.

[0084] The aryl group is not particularly limited, but examples thereof include aryl groups having 6 to 20 carbon atoms. The aryl group may contain two or more rings. A preferred aryl group is a phenyl group.

[0085] The alkyl group and aryl group may contain, if desired, a heteroatom such as a nitrogen atom, oxygen atom or sulfur atom in the molecular chain or ring.

[0086] Furthermore, the alkyl and aryl groups may optionally be substituted with halogen; one or more halogens; 1-6 Alkyl group, C 2-6 Alkenyl group, C 2-6 Alkynyl group, C 3-10 Cycloalkyl groups, C 3-10 Unsaturated cycloalkyl groups, 5-10 membered heterocyclyl groups, 5-10 membered unsaturated heterocyclyl groups, C 6-10 It may be substituted with one or more substituents selected from an aryl group and a 5- to 10-membered heteroaryl group.

[0087] R 272 is a divalent polyether group. That is, R 272 is generally of the following formula: -(R E -O) q - [In the formula, R E is independently in each occurrence a divalent hydrocarbon group having 1 to 20 carbon atoms; q is any integer.] It is expressed as:

[0088] R E is preferably a branched or linear divalent hydrocarbon group. The divalent hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and particularly an alkylene group. E The number of carbon atoms in R may be 1 or more, 2 or more, 3 or more, 5 or more, 8 or more, or 10 or more, and is preferably 2 or more. E may have 20 or less, 15 or less, 10 or less, 6 or less, or 3 or less, preferably 6 or less, more preferably 3 or less.

[0089] In a preferred embodiment, R 272 is expressed by the following formula: -(R E’ O) x -(CH2CH2O) y -(CH(CH3)CH2O) z - [In the formula, R E’ is the above R E and x, y, and z are integers greater than or equal to 0, satisfying x+y+z≧1. -(R E’ O) x - and - (CH2CH2O) y - and -(CH(CH3)CH2O) z The order of - is not limited to the order in the above formula, and may be random. It is expressed as:

[0090] x, y, and z are each an integer of 0 or greater that satisfies x+y+z≧1. The values ​​of x, y, and z are not particularly limited as long as they are integers of 0 or greater that satisfy x+y+z≧1, and examples thereof include 0 to 300, 0 to 100, 0 to 50, 0 to 20, and 0 to 10, respectively.

[0091] In a more preferred embodiment, x is any integer of 0 or greater, and y and z are each an integer of 0 or greater that satisfies y+z≧1. The values ​​of x, y, and z are not particularly limited as long as they satisfy the above conditions, but examples include x being 0 to 100, y being 1 to 300, and z being 1 to 300, x being 0, y being 1 to 100, and z being 1 to 100, etc.

[0092] R 273 is a hydrogen atom or a monovalent organic group.

[0093] In one embodiment, R 273 is a hydrogen atom.

[0094] In one embodiment, R 273 is a monovalent organic group.

[0095] R 273 In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0096] R 25 and R 26 are each independently a hydrogen atom or a monovalent organic group.

[0097] R 25 and R 26 In the formula (B), the monovalent organic group is not particularly limited, and any monovalent organic group may be used as long as it allows the polyether-modified polydimethylsiloxane (B) to exist stably.

[0098] The weight average molecular weight of the polyether-modified polydimethylsiloxane (B) may be, for example, 600 or more, 2,000 or more, 5,000 or more, 7,000 or more, or 10,000 or more. The weight average molecular weight of the polyether-modified polydimethylsiloxane (B) may be, for example, 100,000 or less, 50,000 or less, 30,000 or less, 15,000 or less, 10,000 or less, or 8,000 or less.

[0099] The content of the polyether-modified polydimethylsiloxane (B) is 0.1 to 30 parts by mass, preferably 1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the polymer (A).

[0100] [Aqueous medium] The composition contains a polymer (A), a polyether-modified polydimethylsiloxane (B), and an aqueous medium (C).

[0101] The aqueous medium is water or a mixture of water and an organic solvent (an organic solvent miscible with water) (the amount of the organic solvent is not particularly limited, but is, for example, 50 parts by mass or less, preferably 30 parts by mass or less, and more preferably 520 parts by mass or less per 100 parts by mass of water).

[0102] The aqueous medium is preferably a mixture of water and an organic solvent, which can provide excellent water repellency, slip resistance, and storage stability.

[0103] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., polyhydric alcohols such as alcohols and glycol-based solvents, ethers of polyhydric alcohols (e.g., monoethers), etc.). These may be used alone or in combination of two or more.

[0104] (Amount of aqueous medium) The amount of the aqueous medium is not particularly limited, and may be, for example, 1% by mass or more, 2% by mass or more, 3% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, or 60% by mass or more relative to the water repellent composition. The amount of the aqueous medium may be 80% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less relative to the water repellent composition. The amount of the aqueous medium is preferably 2 to 40% by mass, and more preferably 4 to 30% by mass, relative to the water repellent composition.

[0105] A polymer composition, which is a polymer dispersion, is preferably formed by emulsion polymerization in which monomers are polymerized in the presence of an aqueous medium. The polymer composition is preferably an aqueous dispersion, more specifically, an aqueous dispersion in which polymer particles are dispersed in an aqueous medium. In the dispersion, the average particle size of the hydrocarbon group-containing polymer particles is preferably 0.01 to 200 micrometers, for example, 0.1 to 5 micrometers, and particularly 0.05 to 0.2 micrometers. The average particle size can be measured using a dynamic light scattering device, a laser diffraction particle size distribution analyzer, an electron microscope, or the like.

[0106] The amount of the organic solvent may be 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 40% by weight or more, based on the aqueous medium, and 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, 12.5% ​​by weight or less, 7.5% by weight or less, or 5.0% by weight or less, based on the aqueous medium.

[0107] 〔silicone〕 The water repellent composition of the present disclosure may contain other silicones in addition to the polyether-modified polydimethylsiloxane (B). By including other silicones, the water repellent composition can have both good water repellency and slip resistance.

[0108] Silicones have the formula: (R53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )2-O-] b -Si(R 53 )3(S1) [In the formula, R 51 each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or an alkoxy group having 1 to 40 carbon atoms; R 53 each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a saturated hydrocarbon group having 1 to 40 carbon atoms; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 5 to 200. The polymer may be represented by the formula:

[0109] R 51 and R 53 In the above, the alkyl group having 1 to 40 carbon atoms and the aryl group having 6 to 40 carbon atoms may be unsubstituted or substituted. R 51 and R 53 Specific examples of R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group; a cyclopentyl group, a cyclohexyl group, a cycloheptyl group; a phenyl group, a tolyl group, a naphthyl group, or a group in which some or all of the hydrogen atoms bonded to these groups have been substituted with a halogen atom, an amino group, a cyano group, or the like. 51 and R 53 is preferably a methyl group or an ethyl group. R 51 and R 53 In the above formula, the alkoxy group having 1 to 40 carbon atoms may be linear or branched. Examples of the alkoxy group having 1 to 40 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0110] The silicone may have at least one long chain hydrocarbon group. For example, R 51 At least one of R 53 At least one of or R 51 and R 53 may be a long chain hydrocarbon group, and 51 At least one (for example, one) of the above may be a long-chain hydrocarbon group. Here, the long-chain hydrocarbon group may be a saturated hydrocarbon group having 6 or more, 10 or more, 15 or more, or 20 or more carbon atoms, preferably 10 or more or 23 or more carbon atoms. Here, the hydrocarbon group may be linear or branched, and is preferably an alkyl group. Specific examples of hydrocarbon groups include a hexyl group (6 carbon atoms), an octyl group (8 carbon atoms), a lauryl group (12 carbon atoms), a myristyl group (14 carbon atoms), a stearyl group (18 carbon atoms), a behenyl group (22 carbon atoms), a tricosyl group (23 carbon atoms), a lignoceryl group (tetracosyl group, 24 carbon atoms), a cellotyl group (hexacosyl group, 26 carbon atoms), a monthyl group (octacosyl group, 28 carbon atoms), a melissyl group (triacontane group, 30 carbon atoms), and a dotriacontane group (32 carbon atoms).

[0111] The long-chain hydrocarbon group R is preferred because it is easy to produce industrially and is readily available. 51 and R 53 Other than R 51 and R 53 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0112] a is an integer of equal to or greater than 0. In terms of ease of industrial production and availability, a may be equal to or less than 40, equal to or less than 30, or equal to or less than 20, and is preferably equal to or less than 30.

[0113] The sum of a and b is 5 to 200. From the viewpoints of ease of industrial production, availability, and handling, the sum of a and b is preferably 10 to 100, and more preferably 40 to 60. a may be 0 to 150, for example, 1 to 100. The lower limit of b may be 1, 2, or 3, and the upper limit of b may be 150, 10, or 5.

[0114] When a or b is 2 or more, multiple R 51 and R 52 may be the same or different.

[0115] R 51 and R 53 group (for example, when represented by the following formula (S2), R 51 and R 52 Group and R 53 It is preferred that 50 mol % or more of the total of the alkyl groups) are methyl groups.

[0116] The order of the repeating units bound by a or b is not limited to the order shown in the chemical formula, and can be any order. That is, the silicone may be a random polymer or a block polymer.

[0117] For example, silicones may have the formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )(R 52 )-O-] b -Si(R 53 )3(S2) [In the formula, R 51 each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a long-chain hydrocarbon group; R 52 each independently represents a long chain hydrocarbon group; R 53 each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a long-chain hydrocarbon group; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 5 to 200. The polymer may be represented by the formula: In formula (S2), R 51 and R 53may have an alkyl group having 3 to 40 carbon atoms or an unsaturated hydrocarbon group having 6 to 40 carbon atoms (for example, a hydrocarbon group having an aromatic ring), but it is preferable that it does not have these groups.

[0118] Examples of silicones are: [ka] [In the formula, a represents an integer of 0 to 150, b represents an integer from 1 to 150; (a+b) is 5 to 200, n is an integer of 1 to 36 (preferably n is a long-chain hydrocarbon group).

[0119] Silicone can be synthesized by a conventionally known method, for example, by subjecting silicone having a SiH group to a hydrosilylation reaction with an α-olefin.

[0120] Examples of silicones containing SiH groups include methylhydrogensilicones with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methylhydrogensiloxane. Among these, methylhydrogensilicones are preferred due to their ease of industrial production and availability. Hydrogensilicones (e.g., methylhydrogensilicones) are polydiorganosiloxanes in which a portion of the side chain is substituted with hydrogen, with the hydrogen atoms directly bonded to silicon atoms. When using hydrogensilicones, a catalyst may be used to improve reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine-based catalysts can be used. Metal salts of organic acids are preferred as catalysts, and fatty acids are preferred as organic acids. From the perspective of safety, zinc stearate or the like can be used. The catalyst is preferably used in an amount of 10 to 40% relative to the methylhydrogensilicone, as this enhances its effectiveness. Two or more of amino-modified, epoxy-modified, carboxy-modified, and methylhydrogensilicones may be mixed. All of these silicones have reactive groups, and it is preferable that they have film-forming properties. The term "film-forming ability" refers to the ability of the silicone to form a solid film, rather than an oil or gel film, after being attached to the surface of a fiber in an emulsion state.

[0121] α-olefins are compounds from which long-chain hydrocarbon groups in silicones are derived. Specific examples of α-olefins include 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triacontene, and 1-dotriacontene. The hydrosilylation reaction may be carried out by reacting the above-mentioned silicone having an SiH group with an α-olefin in stages or all at once, if necessary in the presence of a catalyst.

[0122] The amounts of the SiH group-containing silicone and the α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent weight or number average molecular weight of the SiH group-containing silicone.

[0123] Examples of catalysts used in the hydrosilylation reaction include platinum and palladium compounds, with platinum compounds being preferred, such as platinum(IV) chloride.

[0124] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted appropriately. The reaction temperature is, for example, 10 to 200° C., preferably 50 to 150° C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150° C. The hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of inert gases include nitrogen and argon. The reaction proceeds without a solvent, but a solvent may also be used. Examples of solvents include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0125] (reactive silicone) The silicone may include a reactive silicone. Examples of reactive silicones include polysiloxanes having reactive groups in the side chain, one end, both ends, or the side chain and both ends. However, from the viewpoint of achieving excellent slip resistance and water repellency at the same time, polysiloxanes having reactive groups in the side chain and / or both ends may also be used. The reactive silicone is not particularly limited as long as it has a reactive group in the molecule, and examples include amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, and hydrogen-modified silicone. The reactive silicone may be one in which one or more substituents in the above formula (S1) or formula (S2) have been replaced with a reactive group.

[0126] Examples of amino-modified silicones include those having a structure in which an amino group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. The alkylene group preferably has 2 or more carbon atoms. The divalent aromatic group preferably has 6 or more carbon atoms. The amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group. Examples of organic groups having an amino group bonded thereto include the following: 2-aminoethyl group, N-methyl-2-aminoethyl group, N,N-dimethyl-2-aminoethyl group, N-ethyl-2-aminoethyl group, N,N-diethyl-2-aminoethyl group, N,N-methylethyl-2-aminoethyl group, 3-aminopropyl group, N-methyl-3-aminopropyl group, N,N-dimethyl-3-aminopropyl group, N-ethyl-3-aminopropyl group, N,N-diethyl-3-aminopropyl group, and N,N-methylethyl-3-aminopropyl group. These functional groups may be located on the side chains of the polysiloxane or at the terminals.

[0127] Epoxy-modified silicones include those having a structure in which an epoxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Typically, the bond between the organic group and the epoxy group is in the form of a glycidyl ether. Examples of such functional groups include 3-glycidoxypropyl and 2-glycidoxyethyl groups. These functional groups may be present on the side chain or at the terminal of the polysiloxane.

[0128] Examples of carboxy-modified silicones include those having a structure in which a carboxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. The alkylene group preferably has two or more carbon atoms. The divalent aromatic group preferably has six or more carbon atoms. Examples of such functional groups include a 3-carboxypropyl group and a 2-carboxyethyl group. These functional groups may be present on the side chain of the polysiloxane or at the terminal.

[0129] (Silicone resin) The silicone may include a silicone resin. The silicone resin may be RSiO 1 / 2 Unit (M unit), RSiO 3 / 2 Units (T units) and SiO 4 / 2 The silicone resin (3) is a silicone resin consisting of at least one selected from R2SiO 2 / 2 It is preferable that the unit (D unit) is not contained in order to exert the effect of the present invention.

[0130] The silicone resin is preferably in a sol state. Examples of R include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, decyl, cetyl, and stearyl groups. However, in terms of stability when the silicone resin (3) is in a sol state, ease of raw material availability, and cost, R is preferably a methyl group, and it is particularly preferred that 90% or more of all R are methyl groups. Note that different types of groups may be used in combination as R.

[0131] Silicone resin with R2SiO 2 / 2 If the silicone resin contains D units, the low slip properties of the composition may be impaired. Also, if the silicone resin contains only Q units, the water repellency of the composition may be impaired.

[0132] Examples of the silicone resin structure include (i) silicone resins consisting of M units and Q units, (ii) M units, T units and Q units, (iii) M units and T units, (iv) T units and Q units, and (v) silicone resins consisting only of T units. (i) Silicone resins consisting of M units and Q units and (v) silicone resins consisting only of T units are preferred. (i) The molar ratio of M units to Q units (M / Q) in silicone resins consisting of M units and Q units is preferably 0.6 to 1.3, more preferably 0.8 to 1.1. Two or more of these silicone resins may be used in combination.

[0133] The silicone resin (3) may also contain a structural unit containing a hydroxyl group bonded to a silicon atom. Specifically, (HO)RSiO 2 / 2 Units and (HO)2RSiO 1 / 2 Units: (HO)SiO 3 / 2 Units: (HO)2SiO 2 / 2 Units: (HO)3SiO 1 / 2 Some of the hydroxyl groups may be alkoxy groups represented by RO groups.

[0134] As described in Patent No. 3852921, sols containing silicone resins can be obtained by a manufacturing method in which organodisiloxane, tetraalkoxysilane, and their partial hydrolysis condensates are uniformly dispersed and polymerized in water containing a surfactant, or by a manufacturing method in which the following silane compounds are hydrolyzed in water.

[0135] The production method of hydrolyzing a silane compound in water will now be described in detail. Any silane compound can be used as a raw material for production, as long as the hydrolyzable group is chloro or alkoxy, the compound contains one, three, or four hydrolyzable groups, and the compound has an alkyl group that satisfies the above conditions.Specifically, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrichlorosilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrichlorosilane, Trichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrichlorosilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, 2-ethylhexyltrichlorosilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, decyltriethoxysilane, cetyltrichlorosilane, cetyltrimethoxysilane, cetyltriethoxy Silane, stearyl trichlorosilane, stearyl trimethoxysilane, stearyl triethoxysilane, trimethyl chlorosilane, trimethyl methoxysilane, trimethyl ethoxysilane, trimethyl isopropoxysilane, dimethyl ethyl chlorosilane, dimethyl ethyl methoxysilane, dimethyl ethyl ethoxysilane, dimethyl propyl chlorosilane, dimethyl propyl methoxysilane, dimethyl propyl ethoxysilane, dimethyl isopropyl chlorosilane, dimethyl isopropyl methoxysilane, dimethyl isopropyl ethoxysilane, di Usable silane compounds include, but are not limited to, methylhexyl chlorosilane, dimethylhexyl methoxysilane, dimethylhexyl ethoxysilane, dimethyldecyl chlorosilane, dimethyldecyl methoxysilane, dimethyldecyl ethoxysilane, dimethyl cetyl chlorosilane, dimethyl cetyl methoxysilane, dimethyl cetyl ethoxysilane, dimethylstearyl chlorosilane, dimethylstearyl methoxysilane, dimethylstearyl ethoxysilane, and partial hydrolysates thereof.From the viewpoints of operability, ease of distilling off by-products, and ease of obtaining raw materials, it is more preferable to use methoxysilane or ethoxysilane. One or a mixture of two or more of these silane compounds may be used.

[0136] As a method for hydrolyzing a silane compound in water, a commonly known common method can be used, such as a method in which the hydrolysis reaction is carried out while the silane compound is dropped into water, or a method in which water and the silane compound are mixed together and then the hydrolysis reaction is carried out. A hydrolysis catalyst may be used when carrying out the hydrolysis reaction. Conventional catalysts can be used as the hydrolysis catalyst, and it is preferable to use an acidic or alkaline catalyst. In the case of an acidic catalyst, hydrogen halide, carboxylic acid, sulfonic acid, acidic or weakly acidic inorganic salt, solid acid such as ion exchange resin is preferred. In the case of an alkaline catalyst, alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate, alkali metal silanolates such as sodium silanolate and potassium silanolate, amines such as triethylamine, diethylamine, and aniline, and aqueous ammonia can be used. The amount of catalyst added is preferably adjusted so that the pH of the aqueous solution is 2 to 7 or 7 to 12. Furthermore, after completion of the reaction, a neutralizing agent to neutralize the acidic or alkaline catalyst may be added as needed.

[0137] A surfactant may be added to the aqueous solution to disperse the silane compound and the hydrolysis reaction product in water. The surfactant is not particularly limited, but examples include anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, and alkyl phosphates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene oxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and polyoxyethylene fatty acid esters; cationic surfactants such as quaternary ammonium salts and alkylamine acetates; and amphoteric surfactants such as alkyl betaines and alkyl imidazolines. These surfactants can be used alone or in combination. Surfactants that exhibit acidic or alkaline properties can also be used as hydrolysis catalysts. The amount of surfactant added is not particularly limited, but is preferably 1 to 50 parts by weight per 100 parts by weight of the silane compound. Less than 1 part by weight of the surfactant will not be effective, while more than 50 parts by weight may impair the water repellency of the water repellent agent.

[0138] A hydrolysis catalyst and surfactant may be added to a mixture of water and silane compound, if necessary, and the hydrolysis reaction may be carried out at 0 to 90°C for 10 minutes to 24 hours. A neutralization reaction may then be carried out as necessary to obtain a silicone resin. Furthermore, by-products such as alcohols and neutralized salts produced by the hydrolysis reaction may be removed by vacuum distillation or filtration. Various additives may be added to this silicone resin. For example, preservatives, thickeners, etc. may be added depending on the purpose.

[0139] (amount of silicone) The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the polymer. The amount of silicone may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the polymer.

[0140] 〔wax〕 The water repellent composition of the present disclosure may contain a wax. By containing a wax, the water repellent composition can have both water repellency and slip resistance in a good combination.

[0141] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, animal and vegetable wax, and mineral wax. Paraffin wax is preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane), and normal alkenes (e.g., 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane). The number of carbon atoms in the compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500, or 300 to 1000. These may be used alone or in combination of two or more.

[0142] The melting point of the wax may be 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher, preferably 55° C. or higher, more preferably 60° C. or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0143] (amount of wax) The amount of wax may be 0.1 parts by mass or more, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more, relative to 100 parts by mass of polymer (A). The amount of wax may be 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less, relative to 100 parts by mass of polymer (A).

[0144] [Inorganic particles] The water repellent composition of the present disclosure may contain inorganic particles. By including inorganic particles, water repellency and slip resistance can be better imparted. The inorganic particles may be aluminum compounds (e.g., alumina), silicon compounds (e.g., silica), titanium compounds, etc. These may be used alone or in combination of two or more. The inorganic particles may be subjected to a hydrophilic surface treatment or a hydrophobic surface treatment.

[0145] The average primary particle diameter of the inorganic particles may be 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, or 30 nm or more. The average primary particle diameter of the inorganic particles may be 600 nm or less, 400 nm or less, 200 nm or less, 100 nm or less, 40 nm or less, 37.5 nm or less, 35 nm or less, 32.5 nm or less, 30 nm or less, 27.5 nm or less, 25 nm or less, or 22.5 nm or less, preferably 40 nm or less. Being within the above range allows for good water repellency and slip resistance. The average primary particle diameter can be measured using a microscope (scanning electron microscope or transmission electron microscope). Specifically, an arbitrary position on the fabric is observed from above using a microscope at an arbitrary magnification. Next, if the particle shape is spherical, the particle diameter is considered to be the diameter; if the particle shape is non-spherical, the average of the longest and shortest diameters is considered to be the particle diameter (particle size). The particle size of all particles present in the field of view is measured, and then the field of view is moved and the particle size is measured again. This process is repeated until particle sizes are measured at 10 or more points, and the average value is taken as the average primary particle size.

[0146] (amount of inorganic particles) The amount of the inorganic particles may be 0.1 parts by mass or more, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more, relative to 100 parts by mass of the polymer (A). The amount of the inorganic particles may be 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less, relative to 100 parts by mass of the polymer (A).

[0147] [Dispersant] The water repellent composition may contain a dispersant. The dispersant may be a polymer dispersant, preferably a hydrophilic polymer dispersant. Examples of dispersants that can be used include polyvinylpyrrolidone, polyvinyl alcohol, polyglycerin, and polyacrylates. These may be used alone or in combination.

[0148] (amount of dispersant) The amount of the dispersant may be 0.1 parts by mass or more, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more, relative to 100 parts by mass of the polymer (A). The amount of the dispersant may be 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less, relative to 100 parts by mass of the polymer (A).

[0149] [Surfactant] The water repellent composition preferably contains a surfactant. In the water repellent composition, the surfactant may include a nonionic surfactant. By including a surfactant, it is possible to achieve both water repellency and slip resistance in a good balance. Furthermore, the surfactant may include one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. In a preferred embodiment, the water repellent composition contains a nonionic surfactant.

[0150] (nonionic surfactant) The nonionic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the nonionic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0151] Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides.

[0152] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0153] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to hexa-hydric (particularly di- to penta-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0154] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to hexa-hydric (particularly di- to penta-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0155] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamine. An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0156] The polyhydric alcohol may be a dihydric to pentahydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (having, for example, 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0157] The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably 2 to 100. The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.

[0158] The nonionic surfactant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide adduct moiety and the polyalkylene glycol moiety is polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic surfactant preferably has a structure that does not contain an aromatic group in view of environmental issues (biodegradability, environmental hormones, etc.).

[0159] In addition to the above, the nonionic surfactant may be a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), or a sucrose ester of a linear and / or branched fatty acid (saturated and / or unsaturated).

[0160] The nonionic surfactants are those having the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms, R 2 are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is an integer equal to or greater than 2, q is an integer of 0 or 1 or more. The compound may be a compound represented by the formula:

[0161] R 1 R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. 1 Preferred specific examples include a lauryl group, a tridecyl group, and an oleyl group. R 2 Examples of the alkyl group include a propylene group and a butylene group. In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q- may form a polyoxyalkylene chain. The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, and among these, an oxypropylene chain is preferred.

[0162] R 1 In addition to the above, preferred specific examples of include an octyl group, a nonyl group, a trimethylnonyl group, and a stearyl group.

[0163] Specific examples of nonionic surfactants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C 12 -C 16 ) Thiol, Sorbitan Mono Fatty Acid (C7-C 19 ) or alkyl (C 12 -C 18 ) amines and the like.

[0164] In addition to the above, specific examples of nonionic surfactants include sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylate, etc.

[0165] Preferred specific examples of the nonionic surfactant include sorbitan fatty acid esters and polyoxyethylene alkyl ethers.

[0166] The proportion of the polyoxyethylene block can be 5 to 80% by mass, for example 30 to 75% by mass, particularly 40 to 70% by mass, based on the molecular weight of the nonionic surfactant (copolymer). The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic surfactant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. An example of a compound having an HLB of less than 15 is a sorbitan fatty acid ester. An example of a compound having an HLB of 15 or more is a polyoxyethylene alkyl ether. The weight ratio of the compound having an HLB of less than 15 to the compound having an HLB of 15 or more may be 90:10 to 20:80, for example 85:15 to 55:45. The nonionic surfactant may be used alone or in combination of two or more kinds.

[0167] (cationic surfactant) The molecular weight of the cationic surfactant may be in the low molecular weight range (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or may be a polymer type (e.g., a molecular weight of 2000 or more). The molecular weight of the cationic surfactant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0168] The cationic surfactant is preferably a compound having no amide group.

[0169] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene adduct ammonium salt. Specific examples of the cationic surfactant include, but are not limited to, amine salt surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, and quaternary ammonium salt surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride.

[0170] Preferred examples of the cationic surfactant are: R 41 -N + (-R 42 )(-R 43 )(-R 44 )X - [In the formula, R 41 , R 42 , R 43 and R 44 is a hydrocarbon group having 1 to 40 carbon atoms, X is an anionic group. is a compound of R 41 , R 42 , R 43 and R 44 Specific examples of X include alkyl groups (for example, methyl, butyl, stearyl, and palmityl groups). Specific examples of X include halogens (for example, chlorine) and acids (for example, hydrochloric acid and acetic acid). The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0171] The cationic surfactant is preferably an ammonium salt. The cationic surfactant is, for example, a compound represented by the following formula: R 71 p -N + R 72 q X - [In the formula, R 71 is C 12or more (e.g. C 12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 72 is H or a C1-C4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH3 and C2H5 are particularly preferred), X is a halogen atom (for example), a C1-C4 fatty acid base, p is 1 or 2, q is 2 or 3, and p+q=4. R 71 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0172] Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0173] The polymeric cationic surfactant may be any of various polymers (e.g., polyquaternium-1 to 47) having a cationic group (e.g., ammonium group, quaternary ammonium group). Examples of polymeric cationic surfactants include cationic natural products (particularly cationic sugars) such as cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationic guar gum, cationic xanthan gum, and chitosan; and polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0174] (anionic surfactants) The molecular weight of the anionic surfactant may be in the low molecular weight range (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or may be a polymer type (e.g., a molecular weight of 2000 or more). The molecular weight of the anionic surfactant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0175] Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid surfactants, phosphoric acid mono- or diester surfactants, and sulfosuccinate esters.

[0176] (Amphoteric surfactant) The molecular weight of the anionic surfactant may be in the low molecular weight range (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or may be a polymer type (e.g., a molecular weight of 2000 or more). The molecular weight of the anionic surfactant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0177] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0178] The surfactant may be a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant, each of which may be one type or a combination of two or more types.

[0179] (amount of surfactant) The amount of surfactant may be, for example, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more, per 100 parts by mass of polymer (A). The amount of surfactant may be, for example, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, or 3 parts by mass or less, per 100 parts by mass of polymer (A). The amount of surfactant is preferably 2 to 30 parts by mass, and more preferably 5 to 15 parts by mass, per 100 parts by mass of polymer (A).

[0180] [Curing agent] The water repellent composition may contain a curing agent (active hydrogen reactive compound or active hydrogen-containing compound). After the polymer (A) is obtained by polymerization, the curing agent may be added to the water repellent composition.

[0181] The curing agent (crosslinking agent) in the water repellent composition can satisfactorily cure the polymer (A). The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive group of the polymer (A). Examples of the active hydrogen-reactive compound include polyisocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound include hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0182] The curing agent may be a polyisocyanate compound. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates.

[0183] Examples of aliphatic polyisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,03-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-di ... Aliphatic diisocyanates such as isocyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0184] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0185] Examples of araliphatic polyisocyanates include araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0186] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0187] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretimines, isocyanurates, and iminooxadiazinediones. These may be used alone or in combination of two or more.

[0188] These polyisocyanates can be used alone or in combination of two or more.

[0189] As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent.The use of a blocked polyisocyanate compound is preferable for reasons such as its relative stability in an aqueous solution and its usability in the same aqueous solution as the water repellent composition.

[0190] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. The polyisocyanate compounds can be used alone or in combination.

[0191] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether.

[0192] The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound include chloromethyl polystyrene.

[0193] The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid and (poly)methacrylic acid.

[0194] Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide and diacetone alcohol.

[0195] Specific examples of the hydrazide compound include hydrazine, carbohydrazide, and adipic acid hydrazide.

[0196] Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0197] (Amount of hardener) The amount of the curing agent may be 0.1 parts by mass or more, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more, relative to 100 parts by mass of the polymer (A). The amount of the curing agent may be 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, or 1 part by mass or less, relative to 100 parts by mass of the polymer (A).

[0198] The wax, inorganic particles, aqueous medium, dispersant, surfactant, or curing agent described above may be added after the production of polymer (A), or polymer (A) may be produced by polymerizing the monomers of polymer (A) in the presence of the wax, inorganic particles, aqueous medium, dispersant, surfactant, or curing agent described above.

[0199] [Other ingredients] The water repellent composition may contain other components in addition to the above components. After producing the polymer (A), other components may be added. Examples of other components include water and / or oil repellents, antislip agents, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above ingredients, other ingredients may include texture adjusters, fabric softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle-resistant agents, drying speed regulators, crosslinking agents, film-forming agents, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, anti-wrinkle agents after washing, shape retention agents, drape retention agents, ironing improvers, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Chinopal CBS-X), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, and stain removers. Fiber surface modifiers include enzymes such as cellulase, amylase, protease, lipase, and keratinase, and agents that can impart silk texture and functionality such as foam inhibitors and moisture absorption and release properties include silk protein powder, surface-modified products, and emulsified dispersions thereof.Specific examples include K-50, K-30, K-10, A-705, S-702, L-710, and FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos), and stain inhibitors such as nonionic polymeric compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units, such as FR627 manufactured by GOO Chemical Industry and SRC-1 manufactured by Clariant Japan.These may be used alone or in combination.

[0200] (antistatic agent) Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate ester salts, phosphonates, and phosphate ester salts; amphoteric antistatic agents such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, and nonionic antistatic agents such as aminoalcohols and their derivatives, glycerin and its derivatives, and polyethylene glycol and its derivatives. Ion-conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ion-conductive groups may also be used. These may be used alone or in combination.

[0201] (preservatives) Preservatives are mainly used to enhance antiseptic and bactericidal properties and maintain antiseptic properties during long-term storage. Examples of preservatives include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol. The amount of preservative is preferably 0.0001 to 1% by mass relative to the total weight of the water repellent composition. When the amount of preservative is equal to or greater than the lower limit of the above range, the effect of adding the preservative is sufficiently obtained, and when the amount is equal to or less than the upper limit, the storage stability of the water repellent composition is good.

[0202] (ultraviolet absorber) An ultraviolet absorber is a chemical agent that has the effect of protecting against ultraviolet rays, and is a component that absorbs ultraviolet rays and converts them into infrared rays, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0203] (Antibacterial agent) Antibacterial agents are components that have the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors caused by microbial decomposition products. Examples of antibacterial agents include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0204] (Deodorant) Examples of deodorizing agents include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (e.g., zinc complex of trisodium methylglycinediacetate described in WO 2012 / 090580).

[0205] (fragrance) The fragrance is not particularly limited, and lists of usable fragrance raw materials can be found in various documents, such as "Perfume and Flavor Chemicals," Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994); "Synthetic Fragrances: Chemistry and Product Knowledge," by Genichi Indo, The Chemical Daily (1996); "Perfume and Flavor Materials of Natural Origin," by Steffen Arctander, Allured Pub. Co. (1994); "Encyclopedia of Fragrances," edited by the Japan Fragrance Manufacturers Association, Asakura Shoten (1989); "Perfumery Material Performance V.3.3," by Boelens Aroma Chemical Information Service (1996); and "Flower Oils and Floral Compounds in Perfumery," by Danute Lajaujis Anonis, Allured Pub. Co. (1993), each of which is incorporated herein by reference.

[0206] (amount of other ingredients) The amount of the other components may be 0.1 parts by mass or more, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more, relative to 100 parts by mass of the polymer (A). The amount of the other components may be 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less, relative to 100 parts by mass of the polymer (A).

[0207] <Method of producing water repellent composition> The method for producing the water repellent composition may include polymerizing the monomer (a1) in the presence of the polyether-modified polydimethylsiloxane (B) to obtain the polymer (A). By such a method, the water repellent composition of the present disclosure can be obtained.

[0208] Examples of the polymerization method include suspension polymerization and emulsion polymerization, and emulsion polymerization is preferred from the viewpoint of obtaining an emulsion of the polymer (A).

[0209] When emulsion polymerization is employed, first, all or a portion of the monomer (a1) (and the monomer (a2) blended as needed), the polyether-modified polydimethylsiloxane (B), a surfactant, and a liquid medium are mixed to prepare a mixed liquid.

[0210] The surfactant may be added in an amount of, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and for example, 10 parts by mass or less, preferably 5 parts by mass or less, relative to 100 parts by mass of the total amount of the monomer (a1) (and the monomer (a2) added as needed).

[0211] The blending ratio of the liquid medium may be, for example, 100 parts by mass or more, preferably 150 parts by mass or more, and for example, 400 parts by mass or less, preferably 300 parts by mass or less, per 100 parts by mass of the total amount of the monomer (a1) (and the monomer (a2) blended as needed). The liquid medium may be any of those listed above. For example, the liquid medium may be water. In emulsion polymerization, an organic solvent may further be added. The organic solvent may be any of the liquid media listed above. The organic solvent may be a water-soluble glycol solvent, for example, ethylene glycol or propylene glycol.

[0212] In emulsion polymerization, the organic acid listed above may be added. For example, the organic acid may be a carboxylic acid such as acetic acid. The organic acid may be, for example, 0.01 parts by mass or more, 0.1 parts by mass or more, or 1 part by mass or less, 0.5 parts by mass or less, relative to 100 parts by mass of the total amount of the monomer (a1) (and the monomer (a2) added as needed).

[0213] An emulsifier may then be added to this mixture.

[0214] Examples of the emulsifier include known emulsifiers, such as cationic emulsifiers and anionic emulsifiers.

[0215] The above-mentioned surfactants can also be used as the emulsifier.

[0216] The emulsifier may also contain a reactive emulsifier. When the emulsifier contains a reactive emulsifier, the polymer (A) is a polymer containing structural units derived from the reactive emulsifier.

[0217] If the polymer (A) is a polymer containing structural units derived from a reactive emulsifier, the product stability of the aqueous dispersion (repellent composition) is improved without reducing the water repellency.

[0218] The reactive emulsifier is an emulsifying dispersant having radical reactivity, that is, an emulsifier having one or more polymerizable unsaturated groups in the molecule, and is copolymerizable with the above-mentioned monomer. Examples of reactive emulsifiers include the reactive emulsifiers described in JP 2017-25440 A.

[0219] If the reactive emulsifier is one of the reactive emulsifiers described above, the product stability of the aqueous dispersion (repellent composition) is improved without reducing the water repellency. Examples of the reactive emulsifiers described above include polyoxyethylene alkylphenols.

[0220] The emulsifiers can be used alone or in combination of two or more kinds.

[0221] The blending ratio of the emulsifier may be, for example, 0.5 parts by mass or more and, for example, 10 parts by mass or less, relative to 100 parts by mass of the total amount of the monomer (a1) (and the monomer (a2) blended as needed).

[0222] The blending ratio of the emulsifier may be, for example, 0.1% by weight or more and, for example, 5% by weight or less, relative to the water repellent composition.

[0223] After mixing the above-mentioned components, the mixture is stirred and subjected to ultrasonic waves to emulsify the mixture.

[0224] As a method for stirring, for example, a dispersing machine such as a homomixer, an ultrasonic homogenizer, a pressure homogenizer, a milder, or a porous membrane press-in dispersing machine is used, and preferably a homomixer is used.

[0225] Stirring conditions are appropriately set, and when a homomixer is used, the rotation speed is set to, for example, 500 rpm or more and, for example, 10,000 rpm or less. The stirring time is, for example, 1 minute or more and, for example, 30 minutes or less, preferably 25 minutes or less. The stirring temperature is, for example, 50°C or more and, for example, 100°C or less.

[0226] Next, if a portion of the monomers was blended when preparing the above-mentioned mixed solution, the remaining portion of the above-mentioned monomers is blended into this mixed solution.

[0227] Next, a polymerization initiator is added to this mixture.

[0228] Examples of the polymerization initiator include azo compounds such as azobisisobutylamidine dihydrochloride and azobisisobutyronitrile; water-soluble polymerization initiators such as persulfates, for example, potassium persulfate and ammonium persulfate; and oil-soluble polymerization initiators such as organic peroxides, for example, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate. Preferably, the polymerization initiator is an azo compound, and more preferably, azobisisobutyronitrile.

[0229] The blending ratio of the polymerization initiator may be, for example, 0.01 parts by mass or more, for example, 10 parts by mass or less, relative to 100 parts by mass of the total amount of the monomer (a1) (and the monomer (a2) blended as needed).

[0230] If necessary, a chain transfer agent can be added to this mixture.

[0231] Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 30 carbon atoms)), inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite, and preferably lauryl mercaptan.

[0232] The blending ratio of the chain transfer agent may be, for example, 0.01 parts by mass or more and, for example, 10 parts by mass or less, relative to 100 parts by mass of the total amount of the monomer (a1) (and the monomer (a2) blended as needed).

[0233] Then, this mixture is heated to polymerize the monomers.

[0234] The heating conditions include a heating temperature of, for example, 40° C. or higher and, for example, 80° C. or lower, and a heating time of, for example, 1 hour or longer and, for example, 6 hours or shorter.

[0235] This produces an emulsion of the polymer (A), and a water repellent composition containing the polyether-modified polydimethylsiloxane (B) and the polymer (A) (emulsion).

[0236] <Uses of water repellent composition> Examples of applications of the water repellent composition according to the present disclosure include an external treatment agent (surface treatment agent) or an internal treatment agent, a repellent (a water repellent, an oil repellent, or a water and oil repellent, etc., particularly a water repellent), an antifouling agent, a stain release agent, a stripping agent, a release agent (an external release agent or an internal release agent), and the like.

[0237] <Manufacturing method of treated products> A method for making a treatment product according to the present disclosure includes applying a water repellent composition of the present disclosure to a substrate.

[0238] [Processed products] Substrates that can be treated with the water repellent composition of the present disclosure include textiles, stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Various examples of textiles can be mentioned. Examples include natural fibers of animal and plant origin, such as cotton, linen, wool, and silk; synthetic fibers, such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers, such as rayon and acetate; inorganic fibers, such as glass fiber, carbon fiber, and asbestos fiber; and mixtures of these fibers. As an example of a substrate that can be treated with the water repellent composition, a woven or knitted fabric will be described in detail.

[0239] (woven and knitted fabrics) ·Method of manufacturing knitted fabrics The woven or knitted fabric can be obtained by weaving or knitting the mixed and intertwined yarn to obtain a grey fabric, and then post-processing and water-repellent finishing the grey fabric. The weaving and knitting can be carried out using a known loom or knitting machine, and the preparation step prior to the weaving and knitting can also be carried out using known equipment.

[0240] In post-processing, the grey fabric is first scoured and relaxed. Scouring and relaxation can be carried out at a temperature of 80 to 130°C using a continuous or batch method. Usually, it is preferable to carry out the process at a temperature of 100°C or less using a batch method, and it is particularly preferable to carry out the process using a high-pressure jet dyeing machine equipped with a jet nozzle.

[0241] After scouring and relaxing, the woven or knitted fabric is preset. Presetting is usually performed by dry heat treatment at 170 to 200°C for 30 to 120 seconds using a pin tenter. After presetting, the fabric is dyed according to a conventional method, and then subjected to a final setting if necessary.

[0242] After the post-processing, the woven or knitted fabric may be subjected to a water-repellent treatment. In the water-repellent treatment, first, an aqueous solution containing a water repellent (which may be the water-repellent composition of the present disclosure) is prepared. Next, the aqueous solution is applied to the woven or knitted fabric after the post-processing using a padding method, a spray method, a kiss roll coater method, a slit coater method, or the like, and then dry heat treated at 105 to 190°C for 30 to 150 seconds. The aqueous solution may also contain a crosslinking agent, a softener, an antistatic agent, etc., as necessary. After the water-repellent treatment, the woven or knitted fabric may be calendered to further improve the water-repellent performance.

[0243] The woven and knitted fabrics are suitably used for clothing applications, particularly for uniforms, ladies' wear, and sportswear.

[0244] Laminated fabric The woven or knitted fabric of the present disclosure may be provided as a laminated fabric having a moisture-permeable waterproof layer on one side thereof. The moisture-permeable waterproof layer may be laminated directly onto the woven or knitted fabric, or may be laminated onto the woven or knitted fabric via an adhesive layer. When the laminated fabric of the present disclosure is used for clothing or the like, it is positioned so that the woven or knitted fabric side is exposed to rainwater or the like.

[0245] Breathable waterproof layer The moisture-permeable waterproof layer is a layer that covers one side of the woven or knitted fabric and is formed from a resin that has waterproof and moisture-permeable properties.

[0246] The moisture-permeable waterproof layer may be formed by applying a resin (the resin that constitutes the moisture-permeable waterproof layer) directly to the woven or knitted fabric, or may be laminated on one side of the woven or knitted fabric via an adhesive layer, which will be described later. In the present disclosure, a mixed fiber interlaced yarn having minute protrusions due to loops or slack is used in the woven or knitted fabric. Therefore, the protrusions are firmly entangled with the adhesive layer or the moisture-permeable waterproof layer, thereby creating an anchoring effect, making it even more difficult for the woven or knitted fabric and the moisture-permeable waterproof layer to peel off. If a normal woven or knitted fabric (a woven or knitted fabric in which the above-mentioned protrusions are not sufficiently maintained on the surface) is used, the anchoring effect may not be fully exerted, and in such cases, the woven or knitted fabric and the moisture-permeable waterproof layer tend to peel off easily.

[0247] The resin constituting the moisture-permeable waterproof layer is not particularly limited, but is preferably composed primarily of polyurethane resin, and preferably contains polyurethane resin at a ratio of 80% by mass or more. Polyurethane resins are generally suitable for forming resin layers that are moisture-permeable and waterproof. In particular, microporous types are preferred in terms of moisture permeability. However, if the product is expected to be exposed to rain for long periods of time or to be used repeatedly through washing, etc., non-porous moisture-permeable urethane may be used instead of the microporous type.

[0248] As the polyurethane resin, a conventionally known resin obtained by reacting a polyisocyanate component with a polyol component can be used.

[0249] The moisture-permeable waterproof layer may have a microporous structure or a non-porous structure. When the moisture-permeable waterproof layer has a microporous structure, the layer may contain an inorganic fine powder to ensure the desired moisture permeability.

[0250] Examples of inorganic fine powders include fine powders made of silicon dioxide, aluminum dioxide, titanium dioxide, etc. The average primary particle size of the inorganic fine powder is preferably about 7 to 40 nm. The amount of inorganic fine powder is preferably 3 to 50 mass % and more preferably 5 to 50 mass % of the total amount of the moisture-permeable waterproof layer.

[0251] The thickness of the moisture-permeable waterproof layer is preferably 5 μm or more, and more preferably 10 to 30 μm. A thickness within this range provides an excellent balance between waterproofness and moisture permeability, and is also advantageous in terms of texture and tear strength.

[0252] ·Adhesive layer The laminated fabric preferably includes an adhesive layer. That is, the woven / knitted fabric and the moisture-permeable waterproof layer are preferably laminated via an adhesive layer. The reason for this is described below. In the present disclosure, as described above, the woven / knitted fabric has minute protrusions on the surface caused by loops or slack. Therefore, the protrusions are firmly entangled with the adhesive layer, which produces an anchor effect, making it even more difficult for the woven / knitted fabric and the moisture-permeable waterproof layer to peel off.

[0253] Furthermore, when a moisture-permeable waterproof layer is directly laminated to the above-mentioned woven or knitted fabric, for example, by a coating method, the protrusions on the surface of the woven or knitted fabric may penetrate the moisture-permeable waterproof layer, resulting in the formation of pinholes and reduced water resistance and strength. There is also a concern that the coating may not be uniform, resulting in uneven thickness of the moisture-permeable waterproof layer. If attempts are made to smooth the surface of the woven or knitted fabric by, for example, calendaring to prevent this, the protrusions or air-retaining layer may be reduced, resulting in reduced water repellency. Therefore, in the present disclosure, it is preferable to laminate the woven or knitted fabric and the moisture-permeable waterproof layer via an adhesive layer.

[0254] The type of adhesive that constitutes the adhesive layer is not particularly limited, but it is preferable that it is one that has excellent compatibility with the moisture-permeable waterproof layer. For example, if a resin containing polyurethane resin as the main component is selected as the resin that constitutes the moisture-permeable waterproof layer, it is preferable to use an adhesive layer made of a polyurethane-based adhesive. The polyurethane-based adhesive may be any of ether-based, ester-based, polycarbonate-based, etc., but from the viewpoint of imparting excellent moisture permeability, an ether-based adhesive is preferable.

[0255] The adhesive layer may be formed over the entire surface of one side of the woven or knitted fabric, or may be formed in a pattern from the viewpoint of moisture permeability, texture, etc. The pattern shape is not particularly limited, but examples include dots, lines, a grid, a checkerboard pattern, a tortoiseshell pattern, etc., and it is preferable that any of these patterns be uniformly arranged over the entire surface.

[0256] The thickness of the adhesive layer is preferably about 10 to 100 μm, more preferably 20 to 80 μm. If the thickness is less than 10 μm, it is difficult to obtain a durable laminated fabric even if the adhesive occupies a large area, and if it exceeds 100 μm, not only will the manufacturing cost increase but further adhesiveness will also tend to be difficult to expect, both of which are undesirable.

[0257] Lining fabric In the laminated fabric of the present disclosure, a lining fiber fabric may be laminated on the moisture-permeable waterproof layer (on the side of the moisture-permeable waterproof layer opposite to the side on which the woven or knitted fabric of the present disclosure is laminated). The lining fiber fabric can protect the moisture-permeable waterproof layer, thereby providing even better waterproofness (water pressure resistance) and strength. Furthermore, by laminating the lining fiber fabric, the overall elongation of the laminated fabric can be suppressed, which can prevent the protruding parts of the mixed fiber composite yarn from being pulled by elongation of the woven or knitted fabric due to tension during the finishing process after lamination or when worn, and thus can maintain the above-mentioned water repellency at a higher level. Furthermore, laminating the lining fiber fabric can further improve water repellency.

[0258] Examples of lining fiber fabrics include various woven and knitted fabrics. Knitted fabrics are particularly suitable because, compared to woven fabrics, the constituent yarns tend to protrude from the surface, resulting in an uneven surface, and the knitted fabric exhibits a stronger anchoring effect, making it less likely to peel from the moisture-permeable waterproof layer. Tricot knitted fabrics are particularly preferred because they have less stretchability than knitted fabrics with other structures, preventing excessively large stitch gaps and enabling more effective water repellency. Tricot knitted fabrics are also preferred because they can be knitted to produce long gray fabrics with fewer seams, allowing them to be evenly layered on the moisture-permeable waterproof layer.

[0259] The material of the fibers constituting the lining fiber fabric is not particularly limited and can be selected as appropriate, but nylon fiber is preferred. This is because acid dyes are generally used in nylon fibers, which makes it less likely for the disperse dye to migrate and sublimate into the moisture-permeable waterproof layer, a problem that occurs with polyester fibers, etc., which use disperse dyes. The form (long fiber, short fiber, or spun yarn) or fineness of the fibers constituting the lining fiber fabric are not particularly limited and can be selected as appropriate as long as the effects of the present disclosure are not impaired.

[0260] · Properties of laminated fabric The laminated fabric has excellent waterproofness. Suitable examples of waterproofness possessed by the laminated fabric of the present disclosure include a water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method) of, for example, 10,000 mm or more, preferably 15,000 mm or more, more preferably 16,000 mm or more, and particularly preferably 20,000 mm or more. The upper limit of the water level is not particularly limited, but examples include 50,000 mm or 25,000 mm.

[0261] The laminated fabric has excellent moisture permeability. A preferred example of the moisture permeability of the laminated fabric of the present disclosure is a moisture permeability of, for example, 10,000 g / m 2 as measured in accordance with JIS L 1099:2012 B-1 method (potassium acetate method). 2 24 hours or more, preferably 15,000 g / m 2 24 hours or more, more preferably 20,000 g / m 2The upper limit of the moisture permeability is not particularly limited, but for example, 40,000 g / m 2 24h or 35,000g / m 2 ·24h·mm are examples.

[0262] In the laminated fabric, delamination between the woven / knitted fabric and the moisture-permeable waterproof layer is suppressed. In the laminated fabric of the present disclosure, a suitable example of the peel strength between the woven / knitted fabric and the moisture-permeable waterproof layer is, for example, 5 N / 2.54 cm or more, preferably 5 to 50 N / 2.54 cm, more preferably 6 to 30 N / 2.54 cm, and particularly preferably 9 to 25 N / 2.54 cm, as measured according to the method of JIS L 1089. To achieve the peel strength within the above range, for example, a woven / knitted fabric that has not been subjected to calendering may be used, or an adhesive layer may be provided.

[0263] ·Laminated fabric manufacturing method The method for producing the laminated fabric is not particularly limited, but examples thereof include the first and second production methods described below. First manufacturing method: The first manufacturing method includes a step of forming the moisture-permeable waterproof layer by applying a resin that constitutes the moisture-permeable waterproof layer to the surface of a woven or knitted fabric. Second manufacturing method: This method includes the steps of forming an adhesive layer on the woven or knitted fabric or the moisture-permeable waterproof layer, and bonding the woven or knitted fabric and the moisture-permeable waterproof layer together via the adhesive layer.

[0264] It is preferable that the woven / knitted fabric used in the laminated fabric (i.e., the woven / knitted fabric of the present disclosure described above) maintain as many protrusions on the fabric surface as possible. For example, if the woven / knitted fabric is subjected to a calendering process to facilitate coating or other processes, the fine protrusions of the mixed / entangled yarns are crushed to form a flat surface, which may prevent a specific water droplet rolling angle from being achieved. Furthermore, if the calendering process is performed, the air retention layer described above may not be sufficiently maintained, and the desired water repellency may not be achieved. Therefore, it is preferable to carefully consider the calendering conditions. For example, when calendering a woven / knitted fabric, normal conditions (e.g., a temperature of 130°C or higher and a linear pressure of 200 to 20,000 N / cm) may be used so as not to excessively reduce the protrusions of the mixed / entangled yarns. Calendering may also be performed without heating.

[0265] In the first manufacturing method, the resin that constitutes the moisture-permeable waterproof layer can be applied to the surface of the woven or knitted fabric by, for example, a coating method. A knife coater or a comma coater can be used in the coating method. From the viewpoint of providing excellent moisture permeability, it is preferable to obtain the moisture-permeable waterproof layer by a wet method.

[0266] In the second manufacturing method, an example of a method for forming an adhesive layer on a woven or knitted fabric or a moisture-permeable waterproof layer is a lamination method. In the lamination method, a method using a resin solution or a hot melt method can be used to form the adhesive layer. First, a moisture-permeable waterproof layer-forming resin composition (e.g., a resin composition containing a resin and an organic solvent) is applied to the surface of a release material (such as release paper, release cloth, or release film) with a clearance, and a moisture-permeable waterproof layer is formed while adjusting the thickness, followed by heat treatment to completely react and obtain a film. The release material can be removed as appropriate after lamination or aging.

[0267] An adhesive layer is then formed on the woven or knitted fabric or the moisture-permeable waterproof layer. For example, if a resin solution is used, a two-component curing polyurethane resin solution with a viscosity in the range of 500 to 5,000 mPa·s may be applied to the entire surface or in a pattern. The resulting solution is then dried to form an adhesive layer. The woven or knitted fabric and the moisture-permeable waterproof layer are then bonded together via the adhesive layer, and the two are then pressure-bonded or thermocompression-bonded to complete the second manufacturing method.

[0268] On the other hand, in the case of hot melt, it is preferable to use a moisture-curing resin that reacts with moisture in the air, and in practice, it is more preferable to use one that melts in a temperature range of about 80 to 150°C. In this case, first, the hot melt resin is melted while taking into consideration the melting point of the resin and its viscosity when melted. The molten resin is then applied to the woven or knitted fabric or the moisture-permeable waterproof layer and allowed to mature while cooling at room temperature to form an adhesive layer. The woven or knitted fabric and the moisture-permeable waterproof layer are then bonded together via the adhesive layer and pressure-bonded, thereby completing the second manufacturing method.

[0269] It is preferable to adopt the second manufacturing method as the manufacturing method. This is because, when a moisture-permeable waterproof layer is laminated using a coating method, there is a concern that pinholes will occur in the moisture-permeable waterproof layer due to fine protrusions on the surface of the woven or knitted fabric, which will tend to reduce water pressure resistance. Furthermore, when a woven or knitted fabric is subjected to a calendering process in an attempt to form a uniform moisture-permeable waterproof layer, there is a concern that the protrusions or air retaining layer will be reduced and the desired water repellency will not be achieved. Furthermore, since careful examination of the calendering conditions is required separately, the process itself may become complicated.

[0270] Thereafter, a lining fiber fabric can be laminated on the moisture-permeable waterproof layer using any known appropriate method.

[0271] ·Applications of laminated fabric The laminated fabric has excellent water repellency and breathable waterproof properties, and the breathable waterproof layer does not peel off even in harsh environments, making it suitable for use in fields such as uniforms, sportswear, and outdoor products used outdoors.

[0272] [Processing method] The water repellent composition of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by conventionally known methods. The water repellent composition of the present disclosure may be dispersed and diluted in an organic solvent or water, if necessary, and applied to the surface of the substrate by known methods such as dip coating, spray coating, foam coating, etc., followed by drying. After drying, a textile product is obtained to which the solid components of the water repellent composition are attached. If necessary, the composition may be applied together with an appropriate crosslinking agent and cured. Furthermore, the water repellent composition of the present disclosure can also be used in combination with various additives such as water and / or oil repellents, antislip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, and antifoaming agents. Examples of various additives may be the same as those described above under "Other Components" for the water repellent composition. The concentration of the polymer (A) in the treatment agent to be brought into contact with the substrate may be changed appropriately depending on the application, but may be 0.01 to 10% by mass, for example, 0.05 to 5% by mass.

[0273] The pulp base material can be treated by an internal treatment method in which a repellent is added to pulp (e.g., pulp slurry) before papermaking, or an external treatment method in which a repellent is applied to pulp (e.g., pulp product) after papermaking. Examples of internal treatment methods include mixing and immersion, and may include a step of adding a repellent to pulp slurry and stirring and mixing. Examples of external treatment methods include spraying and application, and specific examples include pond-type two-roll size presses, gate-roll type, and rod-metering size presses. The treatment may be an external treatment or an internal treatment. For example, when the pulp base material is paper, the repellent may be coated on the paper, or the solution may be attached or sprayed on the paper, or the repellent may be mixed with the pulp slurry before papermaking.

[0274] [Textile products] There are various examples of textile products that serve as substrates, such as cloth products and paper products. Textile products that serve as substrates are also called fiber substrates.

[0275] Examples of textile products include natural fibers of animal or plant origin such as cotton, linen, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, clothing fabrics, and carpets, but the treatment may also be applied to fibers, yarns, and intermediate textile products (for example, slivers or rovings) in a state before they are made into textiles.

[0276] Examples of paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine paper, recycled corrugated cardboard or deinked recycled paper, paper containers, paper molded articles, etc. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating mediums, neutral white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc.

[0277] The water repellent composition can be applied to a textile by any of the known methods for treating textiles (e.g., fabric) with a liquid. The textile may be immersed in the water repellent composition, or the solution may be applied or sprayed onto the textile. The treated textile is preferably dried and cured by heating to develop water repellency. The heating temperature may be, for example, 80 to 250°C, 100 to 170°C, or 100 to 120°C. In the present disclosure, good performance can be obtained even with low-temperature heating (e.g., 100 to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0278] Alternatively, the water repellent composition may be applied to the textile by a cleaning method, such as by laundering or by dry cleaning.

[0279] The textiles to be treated may be fabrics, including woven fabrics, knitted fabrics, and nonwoven fabrics, clothing fabrics, carpets, etc., but may also be fibers or yarns or intermediate textile products (e.g., slivers or rovings, etc.). The water repellent compositions of the present disclosure are particularly effective in making textiles (e.g., synthetic fibers) water repellent.

[0280] The fibers constituting the textile product may be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers or inorganic fibers. The fibers may be used alone or in combination of two or more types.

[0281] Examples of natural fibers include cotton, flax, cellulose fibers such as pulp, chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as ground wood pulp (GP), pressure-raised ground wood pulp (PGW), and thermomechanical pulp (TMP), chemical pulps such as high-yield unbleached softwood kraft pulp (HNKP; N wood), bleached softwood kraft pulp (NBKP; N wood, NB wood), unbleached hardwood kraft pulp (LUKP; L wood), and bleached hardwood kraft pulp (LBKP; L wood), recycled paper pulps such as deinking pulp (DIP) and waste pulp (WP), and semi-chemical pulp (CP).

[0282] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymer polyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupro, polynosic rayon, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0283] Alternatively, the textile may be leather, and the manufacturing polymer may be applied to the leather from an aqueous solution or emulsion at various stages of leather processing, for example, during wet processing of the leather or during finishing of the leather, to render the leather hydrophobic and oleophobic. Alternatively, the textile product may be paper. The manufacturing polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example, during the drying period of the paper.

[0284] "Treatment" means applying the water repellent composition to a substrate by immersion, spraying, coating, or the like. The treatment allows the polymer (A) and polyether-modified polydimethylsiloxane (B), which are the active ingredients of the water repellent composition, to penetrate into the substrate and / or adhere to the surface of the substrate. In other words, the treatment results in a substrate (e.g., a textile product) to which the polymer (A) and polyether-modified polydimethylsiloxane (B) of the water repellent composition of the present disclosure are adhered.

[0285] [Pretreatment of textile products] The textile product may be pretreated before being treated with the water repellent composition of the present disclosure. Pretreatment of the textile product can impart excellent durability to the textile product after treatment with the water repellent composition.

[0286] Examples of pretreatments for textile products include cationization treatment by reaction with a reactive quaternary ammonium salt, anionization treatment such as sulfonation, carboxylation, and phosphate, acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment.

[0287] The method for pretreating textile products is not limited, and textile products can be pretreated by conventionally known methods. The pretreatment liquid may be dispersed and diluted in an organic solvent or water as necessary, and applied to the surface of the textile product by known methods such as dip coating, spray coating, foam coating, etc., followed by drying. The pH and temperature of the pretreatment liquid may be adjusted depending on the desired degree of treatment. As an example of a method for pretreating textile products, a method for pretreating textile products with a hydrocarbon-based water repellent will be described in detail below.

[0288] The pretreatment method for textile products is to add -SO3M to the fibers. 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) (hereinafter, also referred to as a "specific functional group").

[0289] M 1 Examples of M include H, K, Na, and ammonium ions which may have a substituent. 2 Examples of X include H, K, Na, and an ammonium ion which may have a substituent. 1 or X 2 When is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0290] The fibers containing the specific functional groups (hereinafter, sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following method. (i) A compound having the specific functional group is attached to a fiber material. The attachment of the compound may be in a state where a part of the compound is chemically bonded to a part of the fiber, to the extent that a sufficient amount of the specific functional group remains. (ii) A fiber is prepared in which the specific functional group is directly introduced into the material that constitutes the fiber.

[0291] In the case of (i), for example, functional group-containing fibers can be obtained by a functional group introduction step in which a fiber material is treated with a pretreatment liquid containing one or more compounds having the above-mentioned specific functional groups.

[0292] The material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The form of the fiber material may be any of fibers (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, paper, etc.

[0293] In this embodiment, from the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use textile materials containing polyamide and polyester as raw materials, and it is particularly preferable to use nylons such as nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate and polylactic acid, and mixed fibers containing these.

[0294] Above -SO3M 1 A phenolic polymer can be used as the compound having the formula:

[0033] Such a phenolic polymer can be, for example, one containing at least one compound represented by the following general formula:

[0295] [ka] [In formula (2), X 2 Ha-SO3M 3 (In the formula, M 3represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0296] [ka] [In the formula, M 4 represents a monovalent cation.]

[0297] The above M 3 Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0298] The above M 4 Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0299] The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0300] Above - COOM 2 Examples of compounds having the formula include polycarboxylic acid polymers.

[0301] As the polycarboxylic acid polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer, or a commercially available product can be used.

[0302] Examples of methods for producing polycarboxylic acid polymers include adding a radical polymerization initiator to an aqueous solution of the above-mentioned monomer and / or its salt and reacting the mixture at 30 to 150°C for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, or isopropyl alcohol, or an aqueous solvent such as acetone may be added to the aqueous solution of the above-mentioned monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; redox-based polymerization initiators such as combinations of persulfates and sodium bisulfite; hydrogen peroxide; and water-soluble azo-based polymerization initiators. These radical polymerization initiators may be used alone or in combination. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.

[0303] In addition to the above-mentioned monomers, copolymerizable monomers can be used in radical polymerization. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. Preferred acrylates and methacrylates have a hydrocarbon group having 1 to 3 carbon atoms, which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used alone or in combination.

[0304] The carboxyl group in the polycarboxylic acid polymer may be free or may be neutralized with an alkali metal, an amine compound, etc. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0305] The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000, from the viewpoint of improving the water repellency of the resulting textile product.

[0306] As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (trade name, manufactured by Nicca Chemical Co., Ltd.) and "Ceropol PC-300" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0307] Above -OP(O)(OX 1 )(OX 2 ) includes, for example, phosphate ester compounds represented by the following general formula: [ka] [where, X 1 or X 2 is the same as above, and X 3 represents an alkyl group having 1 to 22 carbon atoms.]

[0308] As the phosphate ester compound, phosphate monoesters, diesters and triesters, in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

[0309] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0310] As the phosphate ester compound, for example, commercially available products such as "Phosphanol ML-200" (trade name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0311] The pretreatment liquid containing one or more compounds having the specific functional group may be, for example, an aqueous solution of the compounds described above. The pretreatment liquid may also contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0312] Methods for treating textile materials with the pretreatment solution include, for example, padding, immersion, spraying, and coating. Examples of padding include methods using padding devices, such as those described on pages 396-397 of "Textile Dyeing and Processing Dictionary" (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of "Color Dyeing Chemistry III" (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating include methods using coating machines, such as those described on pages 473-477 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of immersion include methods using batch dyeing machines, such as those described on pages 196-247 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). These machines include jet dyeing machines, air jet dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, and cheese dyeing machines. Examples of spray treatments include air spraying, which sprays the treatment liquid in a mist form using compressed air, and methods using hydraulic atomization air spraying. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be appropriately adjusted taking into account various conditions, such as the purpose and performance. Furthermore, if the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after application to the fiber material to remove the water. The drying method is not particularly limited, and can be either a dry heat method or a wet heat method. The drying temperature is also not particularly limited, and can be, for example, drying at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment at a temperature of 100 to 180°C for 10 seconds to 5 minutes may be performed after drying.

[0313] When the textile material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as the dyeing. However, when reduction soaping is carried out, there is a risk that the compound having the above-mentioned specific functional group (e.g., a phenolic polymer compound) adsorbed during the process may fall off, so it is preferable to carry out the treatment after reduction soaping after dyeing.

[0314] The treatment temperature in the immersion treatment can be set to 60 to 130° C. The treatment time can be set to 5 to 60 minutes.

[0315] In the functional group introduction step using a pretreatment liquid, the amount of the compound having the specific functional group attached is preferably 1.0 to 7.0 parts by mass per 100 parts by mass of the textile material. Within this range, durable water repellency and texture can both be achieved at high levels.

[0316] The pH of the pretreatment liquid is preferably adjusted to 3 to 5. The pH can be adjusted using a pH adjuster such as acetic acid or malic acid.

[0317] The pretreatment solution may contain a salt in order to effectively adsorb the compound having the specific functional group onto the fiber material by the salting-out effect. Examples of salts that can be used include sodium chloride. Examples of suitable ammonium carbonate include sodium carbonate, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0318] In the functional group introduction step using a pretreatment liquid, it is preferable to remove the compound having the specific functional group that has been treated in excess. An example of a removal method is washing with water. By performing sufficient removal, it is possible to prevent the development of water repellency in the subsequent water repellent treatment from being hindered, and in addition, the feel of the resulting textile product is improved. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fiber before contacting it with a hydrocarbon-based water repellent.

[0319] (ii) An example of a fiber in which the specific functional group is directly introduced into the material that constitutes the fiber is cationic dyeable polyester (CD-PET).

[0320] From the viewpoint of improving the water repellency of the resulting textile product, the functional group-containing fiber preferably has a surface zeta potential of −100 to −0.1 mV, more preferably −50 to −1 mV. The zeta potential of the fiber surface can be measured, for example, using a zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0321] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims. [Example]

[0322] Examples of the present disclosure will be specifically described below, but the present disclosure is not limited to these examples.

[0323] [Water repellency test] The water repellency of the treated test fabric was evaluated according to the spray method of JIS-L-1092 (AATCC-22). The water repellency was evaluated according to the following criteria, where a higher score indicates better water repellency.

[0324] 100 No wetting or water droplets were observed on the surface. 90 The surface did not wet, but small water droplets were observed to adhere. 80 Small individual droplets of water were observed wetting the surface. 70 Half of the surface showed wetting, with small individual wettings observed penetrating the fabric. 50 Wetting was observed over the entire surface. 0 Wetting was observed on the entire front and back surfaces.

[0325] [Slip resistance] The test fabric was subjected to a warp slippage test at a load of 160N in accordance with ISO 13936-2, and seam slippage (mm) was measured. The smaller the seam slippage value, the better the slip resistance.

[0326] [Chalk mark resistance] Each test cloth was placed on a flat surface, and the surface of the test cloth was lightly scratched with a fingernail. The chalk-like scratch marks were visually evaluated. The evaluation criteria were as follows. The results are shown in Table 5. ○: The trace is barely visible. ○△: The trace is faintly visible. △: The trace is visible △×: The trace is slightly dark ×: The trace is dark

[0327] [Preparation of raw materials] (Production Example of Acrylic Polymer-Containing Aqueous Dispersion) Manufacturing Example 1 A 500 ml plastic container was charged with 17 g of a water-soluble glycol solvent as an organic solvent, 110 g of pure water as a liquid medium, 60 g of stearyl acrylate as a long-chain aliphatic hydrocarbon group-containing (meth)acrylate, and 0.6 g of a cationic emulsifier, 1 g of sorbitan fatty acid ester, and 4.4 g of polyoxyethylene alkyl ether as surfactants, and the mixture was heated to 80°C, stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. Next, this emulsified dispersion was transferred to a 500cc four-neck flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux condenser. After nitrogen substitution, 0.1g of lauryl mercaptan was charged and stirred, and then 0.6g of an azo group-containing water-soluble initiator was added. The temperature was raised to 60°C and the reaction was carried out for 4 hours to obtain an aqueous dispersion of a polymer. Pure water was then added to prepare aqueous dispersion 1 with a nonvolatile content of 30%.

[0328] Manufacturing Example 2 Aqueous Dispersion 2 containing an acrylic polymer, a surfactant, and a liquid medium was prepared in the same manner as in Production Example 1, except that the formulation was changed according to Table 1.

[0329] Manufacturing Example 3 A 500 ml plastic container was charged with 30 g of a water-soluble glycol solvent as an organic solvent, 180 g of pure water as a liquid medium, 40 g of stearyl acrylate as a long-chain aliphatic hydrocarbon group-containing (meth)acrylate, and 2 g of a cationic emulsifier, 2 g of a sorbitan fatty acid ester, and 6 g of a polyoxyethylene alkyl as surfactants, and the mixture was heated to 60°C, stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. The emulsion was then transferred to a 500 ml autoclave. After purging with nitrogen, 0.2 g of lauryl mercaptan and 20 g of vinyl chloride were added as a chain transfer agent. 1 g of an azo-containing water-soluble initiator was then added, and the mixture was heated to 60°C and reacted for 4 hours to obtain an aqueous polymer dispersion. This dispersion was then diluted with pure water to prepare aqueous dispersion 3 with a nonvolatile content of 30%.

[0330] Production Example 4 Aqueous Dispersion 4 containing an acrylic polymer, a surfactant, and a liquid medium was prepared in the same manner as in Production Example 3, except that the formulation was changed according to Table 1.

[0331] [Table 1] The numbers in the table are the amount of ingredients (g).

[0332] Manufacturing Example 5 A 500 ml plastic container was charged with 5 g of a water-soluble glycol solvent as an organic solvent, 110 g of pure water as a liquid medium, 50 g of KF-945 (Shin-Etsu Chemical Co., Ltd.) as a polyether-modified polydimethylsiloxane, and 4 g of a cationic emulsifier, 4 g of a sorbitan fatty acid ester, and 2.7 g of a polyoxyethylene alkyl ether as surfactants, heated to 80°C, stirred at 2000 rpm in a homomixer for 1 minute, and then ultrasonically emulsified and dispersed for 15 minutes. This dispersion was further diluted with pure water to prepare aqueous dispersion 5 with a nonvolatile content of 30%.

[0333] [Table 2] The numbers in the table are the amount of ingredients (g).

[0334] Comparative Manufacturing Example 1 A five-neck flask equipped with a nitrogen inlet tube, a thermometer, a stirring rod, a reflux condenser, and a dropping funnel was charged with 120 g of pure water as an aqueous medium and 1 g of Catiogen (registered trademark) TML as a surfactant, and the temperature was raised to 80°C to prepare a mixed solution. The obtained mixed solution was kept at 80°C, and 10 g of a 3 mass% aqueous solution of AAPH (2,2'-azobis(2-methylpropionamidine) dihydrochloride) as a polymerization initiator was added to the mixed solution to prepare a polymerization initiator solution. Meanwhile, 320 g of 2-ethylhexyl acrylate, 70 g of methyl methacrylate, 10 g of acrylamide, 420 g of pure water as an aqueous medium, and 15 g of Catiogen (registered trademark) TML as a surfactant were added to a 1000 ml plastic container, and the mixture was mixed and emulsified using a homomixer to prepare a mixed emulsion. Then, while the temperature inside the five-neck flask containing the polymerization initiator solution was maintained at 80°C, the mixed emulsion and 44 g of a 3% by mass aqueous solution of AAPH (2,2'-azobis(2-methylpropionamidine) dihydrochloride) as a polymerization initiator were simultaneously added dropwise from the funnel to the polymerization initiator solution over a period of 3 hours while stirring, thereby carrying out emulsion polymerization. After the dropwise addition was completed, the temperature inside the five-neck flask was maintained at 80°C for 1 hour while stirring the contents inside the four-neck flask. Thereafter, cooling of the five-neck flask was started while stirring the contents inside the five-neck flask, and the temperature inside the five-neck flask was cooled to 30°C. Through the above steps, comparative aqueous dispersion 1 was obtained.

[0335] Comparative Manufacturing Example 2 Comparative aqueous dispersion 2 was prepared in the same manner as in Comparative Production Example 1, except that the formulation was changed according to Table 3.

[0336] [Table 3] The numbers in the table are the amount of ingredients (g).

[0337] Example 1 Aqueous Dispersion 1 (30% nonvolatile content) prepared in Production Example 1 and KF-640 (Shin-Etsu Chemical Co., Ltd., 100% nonvolatile content) polyether-modified polydimethylsiloxane were mixed to a nonvolatile weight ratio of 86:14, and the resulting mixture was further diluted with tap water to prepare a treatment solution with a nonvolatile content of 0.9%. Polyester fabric, nylon fabric, cotton fabric, and polyester / spandex fabric were immersed in the treatment solution and then squeezed with a mangle. The treated fabrics were passed through a pin tenter at 170°C for 1 minute, dried, and cured. The water repellency of the treated test fabrics was evaluated using the JIS L-1092 spray method. The water repellency results are shown in Table 4.

[0338] [Table 4]

[0339] Examples 2 to 11 A treatment solution with a non-volatile content of 0.9% was prepared in the same manner as in Example 1, except that the blending formulation was changed according to Table 4. This treatment solution was used to treat fabric in the same manner as in Example 1, and a water repellency test was carried out. The results are shown in Table 4.

[0340] Comparative Examples 1 to 4 A treatment solution with a non-volatile content of 0.9% was prepared in the same manner as in Example 1, except that the blending formulation was changed according to Table 4. This treatment solution was used to treat fabric in the same manner as in Example 1, and a water repellency test was carried out. The results are shown in Table 4.

[0341] Examples 11 to 21, Comparative Examples 5 to 8 A treatment solution was prepared in the same manner as in Examples 1 to 11 and Comparative Examples 1 to 4, except that the nonvolatile content was diluted to 1.5%. Polyester and nylon fabrics were immersed in the treatment solution and then squeezed with a mangle. The treated fabrics were passed through a pin tenter at 170°C for 1 minute, dried, and cured. The test fabrics thus treated were subjected to the chalk mark test and seam slippage test described above. The water repellency results are shown in Table 5.

[0342] [Table 5]

[0343] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

Claims

1. Polymer (A), A polyether-modified polydimethylsiloxane (B), and an aqueous medium (C), The polymer (A) has the following formula: CH ２ =C(-R １１ )-C(=O)-O-R １２ [In the formula, R １１ is a hydrogen atom or a methyl group, R １２ is a hydrocarbon group having 9 to 40 carbon atoms. The polymer (A) contains a repeating unit derived from a monomer (a1) represented by the formula: the polymer (A) is a copolymer containing a repeating unit derived from the monomer (a1) and a repeating unit derived from a monomer (a2) different from the monomer (a1), the polymer (A) contains, as the monomer (a2), at least one selected from the group consisting of a repeating unit derived from an amide group-containing hydrophobic monomer and a repeating unit derived from a chloride monomer; Water repellent composition.

2. In the monomer (a1), R １２ The water repellent composition according to claim 1, wherein is a hydrocarbon group having 10 to 30 carbon atoms.

3. The water repellent composition according to claim 2, wherein the polymer (A) contains a repeating unit derived from stearyl acrylate as the monomer (a1).

4. 2. The water repellent composition according to claim 1, wherein the polymer (A) contains a repeating unit derived from stearyl acrylate as the monomer (a1) and a repeating unit derived from a stearyl group-containing amide acrylate as the monomer (a2).

5. 2. The water repellent composition according to claim 1, wherein the polymer (A) comprises a repeating unit derived from stearyl acrylate as the monomer (a1) and a repeating unit derived from vinyl chloride as the monomer (a2).

6. 2. The water repellent composition according to claim 1, wherein the polymer (A) comprises, as the monomer (a1), a repeating unit derived from stearyl acrylate, and, as the monomer (a2), a repeating unit derived from a stearyl group-containing amide acrylate and a repeating unit derived from vinyl chloride.

7. The water repellent composition according to claim 1, wherein the polyether-modified polydimethylsiloxane (B) contains at least one structural unit based on ethylene oxide or propylene oxide.

8. The water repellent composition of claim 1 further comprising a surfactant.

9. The water repellent composition according to claim 8 , wherein the surfactant comprises a nonionic surfactant.

10. 2. A method for producing a water repellent composition according to claim 1, comprising a step of reacting the monomer (a1) in the aqueous medium (C) containing the monomer (a1) and the polyether-modified polydimethylsiloxane (B) to obtain the polymer (A).

11. 2. The method for producing the water repellent composition according to claim 1, comprising a step of reacting the monomer (a1) with the monomer (a2) in the aqueous medium (C) containing the monomer (a1), the monomer (a2), and the polyether-modified polydimethylsiloxane (B) to obtain the polymer (A).

12. A method for producing a textile product, comprising applying the water repellent composition according to any one of claims 1 to 9 to a textile substrate.

13. Before applying the water repellent composition to the fiber substrate, -SO ３ M １ (In the formula, M １ represents a monovalent cation), -COOM ２ (In the formula, M ２ represents a monovalent cation), and -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.

14. A textile product to which the polymer (A) and the polyether-modified polydimethylsiloxane (B) in the water repellent composition according to any one of claims 1 to 9 are attached.

15. -SO ３ M １ (In the formula, M １ represents a monovalent cation), -COOM ２ (In the formula, M ２ represents a monovalent cation), and -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.

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