Water repellent composition

Abstract

To provide a water repellent composition capable of imparting both good water repellency and good slip resistance to a fiber product.SOLUTION: The water repellent composition contains a non-fluorine copolymer (A) which has a repeating unit derived from a hydrophobic monomer (a1) having a C2-40 hydrocarbon group, and a repeating unit derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride. In the non-fluorine copolymer (A), the amount of the repeating unit derived from the monomer (a2) is 1-9 wt.% based on the total of the amount of the repeating unit derived from the monomer (a1) and the amount of the repeating unit derived from the monomer (a2).SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Non-fluorine-based water repellents have been developed to impart water repellency to substrates (especially textile products). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2021 / 132172 [Patent Document 2] JP 2020-189980 A Summary of the Invention [Problem to be solved by the invention]

[0004] When conventional water repellents are used in textile products, there is a risk that the stitching may slip, reducing the reliability of the textile product.

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

[0006] The present disclosure includes the following aspects: [Section 1] A non-fluorinated copolymer (A) containing a repeating unit derived from a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms, and a repeating unit derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride, The water repellent composition, wherein in the non-fluorinated copolymer (A), the amount of the repeating units derived from the monomer (a2) is 1 to 9 wt % based on the total amount of the repeating units derived from the monomer (a1) and the repeating units derived from the monomer (a2). [Section 2] The hydrocarbon group in the hydrophobic monomer (a1) is a linear alkyl group having 10 or more carbon atoms. Item 2. The water repellent composition according to item 1, [Section 3] The hydrophobic monomer (a1) has the formula: CH2=C(-R 12 )-C(=O)-Y 11 -(R 11 ) k [In the formula, R 11 is a hydrocarbon group having 2 to 40 carbon atoms, R 12 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 11 represents a divalent to tetravalent group consisting of at least one selected from a direct bond, a divalent to tetravalent hydrocarbon group having 1 carbon atom, -CH-, -O-, -C(=O)-, -S(=O)2-, and -NR'- (R' represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), k is 1 to 3. Item 3. The water repellent composition according to item 1 or 2, wherein the compound is represented by the formula: [Section 4] Item 4. The water repellent composition according to any one of items 1 to 3, which contains silicone. [Section 5] Item 5. The water repellent composition according to Item 4, wherein the amount of the silicone is 0.1 to 10 parts by mass per 100 parts by mass of the non-fluorinated copolymer (A). [Section 6] 6. The water repellent composition according to any one of items 1 to 5, wherein in the non-fluorinated copolymer (A), an amount of the repeating units derived from the monomer (a2) is 3 to 7 wt % based on a total amount of the repeating units derived from the monomer (a1) and the repeating units derived from the monomer (a2). [Section 7] Item 7. The water repellent composition according to any one of items 1 to 6, further comprising an isocyanate derivative (B). [Section 8] Item 8. The water repellent composition according to item 7, wherein the isocyanate derivative (B) has an alkyl group having 12 to 30 carbon atoms. [Section 9] Item 9. The water repellent composition according to item 7 or 8, wherein the isocyanate derivative (B) is a polyurethane. [Section 10] Item 10. The water repellent composition according to any one of Items 7 to 9, wherein the amount of the isocyanate derivative (B) is 0.1 to 10 parts by mass per 100 parts by mass of the non-fluorinated copolymer (A). [Section 11] The water repellent composition according to any one of Items 7 to 10, wherein the isocyanate derivative (B) is a compound obtained by reacting at least one active hydrogen compound selected from the group consisting of hydrocarbon alcohols, sugar alcohol modifications, and hydroxy acid modifications with at least one raw material isocyanate selected from the group consisting of acyclic aliphatic polyisocyanates and derivatives thereof. [Section 12] The hydrophobic monomer (a1) has the formula: CH2=C(-R 12 )-C(=O)-Y 11 -(R 11 ) k [In the formula, R 11 is a hydrocarbon group having 2 to 40 carbon atoms, R 12 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 11 represents a divalent to tetravalent group consisting of at least one selected from a direct bond, a divalent to tetravalent hydrocarbon group having 1 carbon atom, -CH-, -O-, -C(=O)-, -S(=O)2-, and -NR'- (R' represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), k is 1 to 3. A compound represented by the formula: Item 2. The water repellent composition according to Item 1, wherein in the non-fluorinated copolymer (A), the amount of the repeating units derived from the monomer (a2) is 3 to 7 wt % based on the total amount of the repeating units derived from the monomer (a1) and the repeating units derived from the monomer (a2). [Section 13] The hydrophobic monomer (a1) has the formula: CH2=CH-C(=O)-Y 11 -R 11 [In the formula, R 11 is an alkyl group having 12 to 25 carbon atoms, Y 11 is -O- or -O-(CH2) m -NH-C(=O)-, and m is an integer of 2 or 4. the chloride monomer (a2) is vinyl chloride, Item 2. The water repellent composition according to Item 1, wherein, in the non-fluorinated copolymer (A), the amount of the repeating units derived from the monomer (a2) is 3 to 7 wt % based on the total amount of the repeating units derived from the monomer (a1) and the repeating units derived from the monomer (a2). [Section 14] Item 14. A method for producing a textile product, comprising applying the water repellent composition according to any one of items 1 to 13 to a textile substrate. [Section 15] Prior to 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 2each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms), [Section 16] 16. A textile product having the non-fluorinated copolymer (A) in the water repellent composition according to any one of items 1 to 15 adhered thereto. [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 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms), Effect of the Invention

[0007] The water repellent composition of the present disclosure can impart both good water repellency and good slip resistance to a substrate (particularly a textile product). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] <Terminology> As used herein, the term "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. The term "n-valent organic group" refers to an n-valent group containing carbon. Such an organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. The derivative of a hydrocarbon group 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 a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but includes, for example, C 1-20 Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. 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] In this specification, when a term (symbol) that may occur multiple times in a chemical structure is defined, the definition applies independently at each occurrence, unless otherwise stated, regardless of whether "independently at each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated.

[0011] It should be understood that the chemical structures illustrated herein do not encompass chemical structures that would be recognized by those of ordinary skill in the art as being chemically impossible or extremely unstable.

[0012] <Water repellent composition> The water-repellent composition of the present disclosure includes a non-fluorinated copolymer (A) containing a repeating unit derived from a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms, and a repeating unit derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride. In the non-fluorinated copolymer (A), the amount of the repeating unit derived from the monomer (a2) is 1 to 9 wt % based on the total amount of the repeating unit derived from the monomer (a1) and the repeating unit derived from the monomer (a2). The water-repellent composition of the present disclosure is adhered to a substrate (particularly a textile product) and can impart both good water repellency and good slip resistance to the substrate.

[0013] The water repellent composition may further contain an isocyanate derivative (B). The water repellent composition may further contain other components (such as silicone, wax, organic acid, surfactant, organic solvent, etc.).

[0014] [(A) Fluorine-free copolymer] The fluorine-free copolymer (A) has no fluorine atoms.

[0015] The non-fluorinated copolymer (A) is A repeating unit derived from a hydrophobic monomer (a1), and Repeating units derived from chloride monomer (a2) The non-fluorinated copolymer (A) further comprises Cyclic hydrocarbon group-containing monomer (a3), and / or Crosslinkable monomer (a4) The fluorine-free copolymer (A) may contain another monomer (a5).

[0016] ((a1) Hydrophobic monomer) The hydrophobic monomer (a1) has one ethylenically unsaturated double bond and a hydrocarbon group having 2 to 40 carbon atoms.

[0017] The hydrophobic monomer (a1) 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, especially an alkyl group. The hydrocarbon group may be linear or branched, and is preferably linear. 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, and is 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, and is preferably 30 or less.

[0018] The hydrophobic monomer (a1) has the formula: CH2=C(-R 12 )-C(=O)-Y 11 -(R 11 ) k [In the formula, R 11 is a hydrocarbon group having 2 to 40 carbon atoms, R 12 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 11 represents a divalent to tetravalent group consisting of at least one selected from a direct bond, a divalent to tetravalent hydrocarbon group having 1 carbon atom, -CH-, -O-, -C(=O)-, -S(=O)2-, and -NR'- (R' represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), k is 1 to 3. The monomer may be represented by the formula:

[0019] R 11 is 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, especially an 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, a long-chain alkyl group of a certain length exhibits high liquid repellency due to its crystallinity. Therefore, it 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. R 11 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. 11 may have 40 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 12 or less carbon atoms.

[0020] k is 1, 2 or 3. 11 In the case where Y has a tetravalent hydrocarbon group having one carbon atom, k=3. 11 In the case where Y has a trivalent hydrocarbon group having one carbon atom, k=2. 11 does not have a trivalent or tetravalent hydrocarbon group having one carbon atom (for example, Y 11has (for example, 1 to 6) divalent hydrocarbon groups (-CH2-) having 1 carbon atom, then k=1.

[0021] R 12 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. 12 Examples of R are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. 12 is preferably a hydrogen atom, a methyl group, or a chlorine atom. 12 More preferably, R is a methyl group. 12 By using a methyl group, higher liquid repellency can be obtained. 12 may be a hydrogen atom, particularly from the standpoint of reactivity.

[0022] Y 11 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.

[0023] Y 11 -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' is independently a direct bond, -O-, -NR'- (R' is 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 1 is independently an integer of 0 to 5, and -C6H4- is a phenylene group). Y 11 It is preferred that is not exclusively a divalent hydrocarbon group.

[0024] Y 11 Specific examples of -O-, -NH-, -O-C(=O)-, -NH-C(=O)-, -O-C(=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 -O-C(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -O-C(=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 -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, or -NH-(CH2) m -NH-C6H4- [wherein, m is an integer of 1 to 5, particularly 2 or 4].

[0025] Y 11 -O-, -NH-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -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 11 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)-.

[0026] Y 11 is -O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, or -O-(CH2) m It is more preferable that the group is —NH—C(═O)—, wherein m is an integer of 1 to 5, particularly 2 or 4.

[0027] Y 11is particularly preferably -O- or -O-(CH2)2-NH-C(=O)-.

[0028] The hydrophobic monomer (a1) preferably does not have a reactive group or a hydrophilic group. Examples of reactive groups are epoxy groups, chloromethyl groups, bromomethyl groups, iodomethyl groups, isocyanate groups, and blocked isocyanate groups. Examples of hydrophilic groups are hydroxyl groups, polyalkylene oxide groups, amino groups, carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, alkali metal or alkaline earth metal bases of carboxylic acid, sulfonic acid, and phosphoric acid, chlorine or bromine, and ammonium bases with iodine ions as counter anions, and other ionic groups. Here, the reactive group and the hydrophilic group may overlap each other.

[0029] The hydrophobic monomer (a1) may have a water solubility 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 at 25° C., preferably 3 g / L or less. The homopolymer of the hydrophobic monomer (a1) may have a water solubility 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 at 25° C., preferably 3 g / L or less.

[0030] The water contact angle of the homopolymer of the hydrophobic monomer (a1) may be 75° or more, 80° or more, 85° or more, 90° or more, 95° or more to 100° or more, 101° or more, 103° or more, 105° or more, 110° or more, 115° or more, or 120° or more, preferably 90° or more or 100° or more. The water contact angle of the homopolymer of the hydrophobic monomer (a1) may be 160° or less, 150° or less, 140° or less, 130° or less, 125° or less, or 110° or less. It is preferable that the water contact angle is in the above range from the viewpoint of the liquid repellency of the copolymer, particularly water repellency. The water contact angle of the homopolymer may be a value obtained by spin-coating a chloroform solution having a solid content concentration of 1.0% of the homopolymer on a silicon wafer substrate, dropping 2 μL of water on the coating film, and measuring the contact angle 1 second after the drop is applied.

[0031] Specific examples of the hydrophobic monomer (a1) are as follows: The compound of the following chemical formula is an acrylic compound in which the α-position is a hydrogen atom, but it may be a methacrylic compound in which the α-position is a methyl group, or an α-chloroacrylic compound in which the α-position is a chlorine atom. 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 H2n+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]

[0032] Preferred specific examples of the hydrophobic monomer (a1) 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, CH2=CHC(=O)OC2H4NHSO2C 18 H 37 These may be used alone or in combination of two or more.

[0033] From the viewpoint of liquid repellency, the hydrophobic monomer (a1) may contain a hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group. A combination of a hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group and a hydrophobic monomer (a1) not having an amide group, a urea group, or a urethane group may also be used. Examples of the hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group include a hydrophobic monomer (a1) having a CH2=C(-R 12 )-C(=O)-O-(CH2) m -NH-C(=O)-R 11 , CH2=C(-R 12 )-C(=O)-O-(CH2) m -OC(=O)-NH-R 11, CH2=C(-R 12 )-C(=O)-O-(CH2) m -NH-C(=O)-OR 11 , and CH2=C(-R 12 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R 11 The hydrophobic monomer (a1) is CH2=C(-R 12 )-C(=O)-O-(CH2) m -NH-C(=O)-R 11 may include:

[0034] ((a2) Chloride monomer) The fluorine-free copolymer (A) contains a repeating unit derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride. The chloride monomer (a2) is preferably vinyl chloride.

[0035] ((a3) Cyclic Hydrocarbon Group-Containing Monomer) The fluorine-free copolymer (A) may have a repeating unit derived from a cyclic hydrocarbon group-containing monomer (a3). The cyclic hydrocarbon group-containing monomer (a3) ​​is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.

[0036] The cyclic hydrocarbon group-containing monomer (a3) ​​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.

[0037] 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 straight-chain or branched-chain hydrocarbon group).

[0038] 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.

[0039] 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 in which one or more hydrogen atoms have been removed from these groups (e.g., cyclohexylene, adamantylene, phenylene, naphthylene, etc.), and groups which are substitution products thereof.

[0040] Specific examples of the cyclic hydrocarbon group-containing monomer (a3) ​​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.

[0041] ((a4) Crosslinkable monomer) The non-fluorinated copolymer (A) may have a repeating unit derived from a crosslinkable monomer (a4). The crosslinkable monomer (a4) is a monomer capable of imparting crosslinkability to the copolymer, and may have at least two selected from the group consisting of reactive groups and olefinic carbon-carbon double bonds. The crosslinkable monomer (a4) 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.

[0042] The crosslinkable monomer (a4) 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.

[0043] 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.

[0044] Specific examples of the crosslinkable monomer (a4) 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.

[0045] ((a5) Other monomers) The fluorine-free copolymer (A) may contain a repeating unit derived from a monomer (a5) other than the monomers (a1) to (a4).

[0046] Specific examples of the other monomer (a5) include, for example, ethylene, halogenated olefin, vinyl acetate, acrylonitrile, alkoxy polyalkylene glycol (meth)acrylate, and vinyl alkyl ether. The other non-fluorine monomer is not limited to these examples. These may be used alone or in combination of two or more.

[0047] (Polymer Composition) The amount of the repeating units derived from the hydrophobic monomer (a1) may be 50% by weight or more, 60% by weight or more, 65% by weight or more, 70% by weight or more, 75% by weight, 80% by weight or more, or 85% by weight or more, based on the non-fluorinated copolymer (A). The amount of the repeating units derived from the hydrophobic monomer (a1) may be 99% by weight or less, 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 non-fluorinated copolymer (A).

[0048] The ratio of the hydrophobic monomer (a1) having an amide group, urea group or urethane group in the repeating units derived from the hydrophobic monomer (a1) 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 ratio of the hydrophobic monomer (a1) having an amide group, urea group or urethane group in the repeating units derived from the hydrophobic monomer (a1) may be 100% by weight or less, 90% by weight or less, 80% by weight or less, or 70% by weight or less.

[0049] The amount of the repeating unit derived from the chloride monomer (a2) may be 1% by weight or more, 2% by weight or more, 3% by weight or more, 4% by weight or more, or 5% by weight or more, based on the non-fluorine-containing copolymer (A). The amount of the repeating unit derived from the chloride monomer (a2) may be 15% by weight or less, 13% by weight or less, 11% by weight or less, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, or 5% by weight or less, based on the non-fluorine-containing copolymer (A).

[0050] In the fluorine-free copolymer (A), the amount of the repeating units derived from the chloride monomer (a2) may be 1 wt % or more, 2 wt % or more, 3 wt % or more, 4 wt % or more, or 5 wt % or more, preferably 3 wt % or more, based on the total amount of the repeating units derived from the hydrophobic monomer (a1) and the repeating units derived from the chloride monomer (a2).

[0051] In the fluorine-free copolymer (A), the amount of repeating units derived from the chloride monomer (a2) may be 9 wt % or less, 8 wt % or less, 7 wt % or less, 6 wt % or less, or 5 wt % or less, preferably 7 wt % or less, more preferably 5 wt % or less, based on the total amount of repeating units derived from the hydrophobic monomer (a1) and the amount of repeating units derived from the chloride monomer (a2).

[0052] The amount of the repeating unit derived from the cyclic hydrocarbon group-containing monomer (a3) ​​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 non-fluorinated copolymer (A). The amount of the repeating unit derived from the cyclic hydrocarbon group-containing monomer (a3) ​​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 non-fluorinated copolymer (A).

[0053] The amount of the repeating units derived from the crosslinkable monomer (a4) 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 non-fluorine-containing copolymer (A). The amount of the repeating units derived from the crosslinkable monomer (a4) 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 non-fluorine-containing copolymer (A).

[0054] The amount of the repeating units derived from the other monomer (a5) 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 non-fluorinated copolymer (A). The amount of the repeating units derived from the other monomer (a5) 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 non-fluorinated copolymer (A).

[0055] The amount of the repeating units derived from the chloride monomer (a2) may be 1 part by weight or more, 3 parts by weight or more, 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, based on 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1). 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, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, or 6 parts by weight or less, based on 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1).

[0056] The amount of the repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​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 (a1). The amount of the repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​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 (a1).

[0057] The amount of the repeating units derived from the crosslinkable monomer (a4) 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 (a1). The amount of the repeating units derived from the crosslinkable monomer (a4) 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 (a1).

[0058] The amount of the repeating units derived from the other monomer (a5) 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 (a1). The amount of the repeating units derived from the other monomer (a5) 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 (a1).

[0059] [(B) Isocyanate Derivatives] The isocyanate derivative (B) is a compound obtained by reacting an active hydrogen compound with a raw material isocyanate, and has a portion derived from the active hydrogen-containing compound and a portion derived from the raw material isocyanate. Unlike an isocyanate-based curing agent, the isocyanate derivative (B) does not usually have an isocyanate group.

[0060] The isocyanate derivative (B) has -NHCO- formed by the reaction of an active hydrogen compound with a raw material isocyanate (here, -NHCO- may be a part of a urethane group or a urea group). -NHCO- is a group formed by the reaction of an active hydrogen-containing group (typically a hydroxyl group) of the compound (a) with an active hydrogen-reactive group (typically an isocyanate group) of the compound (b). The isocyanate derivative (B) is typically a urethane (particularly a polyurethane).

[0061] The isocyanate derivative (B) may have a hydrocarbon group having 6 to 40 carbon atoms. The hydrocarbon group having 6 to 40 carbon atoms may be a monovalent hydrocarbon group. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched, cyclic or linear, more preferably linear, particularly linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, and is preferably 10 or more, 12 or more, or 16 or more. The number of carbon atoms in the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and is preferably 30 or less, 25 or less, or 20 or less.

[0062] The isocyanate derivative (B) may have an alkyl group having 12 to 30 carbon atoms. The alkyl group having 12 to 30 carbon atoms may be branched or linear, more preferably chain-like, and particularly linear. The alkyl group in the isocyanate derivative (B) may be 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 12 or more, or 16 or more. The alkyl group in the isocyanate derivative (B) may be 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0063] The weight average molecular weight of the isocyanate derivative (B) may be 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more. The weight average molecular weight of the isocyanate derivative (B) may be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 300000 or less, 100000 or less, or 5000 or less.

[0064] The water contact angle of the isocyanate derivative (B) may be 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, 100° or more, 105° or more, 110° or more, or 115° or more. The water contact angle of the isocyanate derivative (B) may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the isocyanate derivative (B) has a water contact angle equal to or greater than the above lower limit, it can impart good water repellency to the substrate. The water contact angle is the static contact angle of the isocyanate derivative (B) with respect to the spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop lands.

[0065] [Active hydrogen compounds] The active hydrogen compound contains an active hydrogen group that reacts with an isocyanate group.

[0066] Examples of the active hydrogen group include a hydroxy group, an amino group, and a carboxyl group, and typically a hydroxy group.

[0067] [(α1) Hydrocarbon alcohol] The active hydrogen compound may be a hydrocarbon alcohol (α1) composed of a hydrocarbon group and a hydroxyl.

[0068] The hydrocarbon group in the hydrocarbon alcohol (α1) may be the above-mentioned hydrocarbon group having 6 to 40 carbon atoms, and the above explanation is incorporated herein. The hydrocarbon group in the hydrocarbon alcohol (α1) may be preferably the above-mentioned alkyl group having 12 to 30 carbon atoms, and the above explanation is incorporated herein.

[0069] Additionally, the hydrocarbon alcohol (α1) preferably has one hydroxy group per molecule.

[0070] Examples of the hydrocarbon alcohol (α1) include linear saturated hydrocarbon group-containing alcohols such as n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol, and eicosanol; branched saturated hydrocarbon group-containing alcohols such as isomyristyl alcohol, isocetyl alcohol, isostearyl alcohol, and isoicosyl alcohol; linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, icosenyl alcohol, docosenyl alcohol, tetracosenyl alcohol, hexacosenyl alcohol, and octacosenyl alcohol; and branched unsaturated hydrocarbon group-containing active hydrogen compounds such as phytol.

[0071] Here, linear saturated hydrocarbon group-containing alcohol and linear unsaturated hydrocarbon group-containing alcohol may be used in combination, and when linear saturated hydrocarbon group-containing alcohol and linear unsaturated hydrocarbon group-containing alcohol are used in combination, the blending ratio of linear saturated hydrocarbon group-containing alcohol is, for example, 40 parts by weight or more, preferably 55 parts by weight or more, more preferably 70 parts by weight or more, and for example, 90 parts by weight or less, preferably 80 parts by weight or less, based on 100 parts by weight of the total amount of linear saturated hydrocarbon group-containing alcohol and linear unsaturated hydrocarbon group-containing alcohol. The blending ratio of linear unsaturated hydrocarbon group-containing alcohol is, for example, 10 parts by weight or more, preferably 20 parts by weight or more, and for example, 60 parts by weight or less, preferably 45 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the total amount of linear saturated hydrocarbon group-containing alcohol and linear unsaturated hydrocarbon group-containing alcohol. When the blending ratio of the linear saturated hydrocarbon group-containing alcohol is equal to or higher than the above lower limit, the crystallinity of the hydrocarbon group is improved, and as a result, the water repellency of the water-repellent treated object treated with this water repellent composition can be improved.

[0072] [(α2) sugar alcohol / hydroxy acid modified] The active hydrogen compound may be a sugar alcohol / hydroxy acid modification (α2), which is a sugar alcohol / hydroxy acid (sugar alcohol and / or hydroxy acid) modified with a hydrocarbon group having 6 to 40 carbon atoms. The type of sugar alcohol / hydroxy acid is not limited and may be cyclic or acyclic. Examples of sugar alcohols include monosaccharides, reducing sugars, amino sugars, aldonic acids, and aldonic acid lactones, and examples of hydroxy acids include hydroxy polycarboxylic acids. The sugar alcohol / hydroxy acid may be a substance present in a living body. Examples of sugar alcohols / hydroxy acids include, but are not limited to, compounds derived from aldoses and ketoses, such as tetroses, pentoses, hexoses and heptoses, and specific examples include glucose, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, gulose, galactose, talose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol, threitol, glucopyranose, mannopyranose, glyceraldehyde, erythritol, threitol, glucopyranose, glyceraldehyde, erythritol ... Examples of the sugar alcohol / hydroxy acid include talopyranose, allopyranose, altropyranose, idopyranose, gropyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fucitol, iditol, inositol, pentaerythritol, dipentaerythritol, volemitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, citric acid, gluconic acid lactone, glyceric acid lactone, xylonic acid lactone, glucosamine, galactosamine, or mixtures thereof. The number of carbon atoms of the sugar alcohol / hydroxy acid may be 2 or more, 4 or more, or 6 or more, and may be 30 or less, 20 or less, or 10 or less. The average OH value of the compound (α2) may be in the range of more than 0 to about 230, preferably about 10 to about 175, and most preferably about 25 to about 140.

[0073] The number of hydrocarbon groups having 6 to 40 carbon atoms in the sugar alcohol / hydroxy acid modified product (α2) may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more. The number of hydrocarbon groups having 6 to 40 carbon atoms in the sugar alcohol / hydroxy acid modified product (α2) may be 12 or less, 9 or less, 6 or less, or 3 or less. The hydrocarbon groups in the sugar alcohol / hydroxy acid modified product (α2) may be the above-mentioned hydrocarbon groups having 6 to 40 carbon atoms, and the above explanation is incorporated herein. The sugar alcohol / hydroxy acid modified product (α2) may have an alkyl group having 12 to 30 carbon atoms. The above explanation is incorporated herein for the alkyl group having 12 to 30 carbon atoms.

[0074] In the sugar alcohol / hydroxy acid modified compound (α2), at least one active hydrogen atom (e.g., a hydrogen atom in an OH group or a carboxyl group) of the sugar alcohol and / or the hydroxy acid is represented by -R α2 , -C(O)R α2 , -(CH2CH2O) n (CH(CH3)CH2O) m R α2 , -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 or mixtures thereof, wherein R α2 is a hydrogen atom or a hydrocarbon group having 6 to 40 carbon atoms, each n is independently 0 to 20, each m is independently 0 to 20, and m+n may be greater than 0. Compound (α2) has at least one active hydrogen, and for example, in the sugar alcohol / hydroxy acid modified product, at least one (1 or more) of the active hydrogens of the sugar alcohol / hydroxy acid may be unmodified, and the active hydrogen (e.g., -OH group) may react with an active hydrogen reactive group (particularly an isocyanate group) of compound (b) to form -NHCO-. The carbon number of 6 to 40 in the sugar alcohol / hydroxy acid modified product (α2) may be preferably the above-mentioned alkyl group having 12 to 30 carbon atoms, and the above explanation is incorporated herein.

[0075] ((α21) Sorbitan modification) The sugar alcohol / hydroxy acid modified product (α2) may be a sorbitan modified product (α21) in which sorbitan is modified with a hydrocarbon group having 6 to 40 carbon atoms, and may in particular be an alkyl sorbitan. α2 , -C(O)R α2 , -(CH2CH2O) n (CH(CH3)CH2O) m R α2 , -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 or a mixture thereof (wherein R α2 is a hydrocarbon group with 6 to 40 carbon atoms. For example, sorbitan is -C(O)R α2 The sorbitan modified product (α21) may be a mono-, di-, or tri-substituted compound. Here, the sorbitan may contain an amount of sorbitol, isosorbide, or other intermediates or by-products. The hydrocarbon group in the sorbitan modified product (α21) may be the above-mentioned hydrocarbon group having 6 to 40 carbon atoms, and the above explanation is incorporated herein. The sorbitan modified product (α21) may have an alkyl group having 12 to 30 carbon atoms. The above explanation is incorporated herein for the alkyl group having 12 to 30 carbon atoms. Commercially available sorbitans such as SPAN can be used as the alkyl sorbitan.

[0076] In one embodiment, at least one active hydrogen substituent is -C(O)R α2 R may be α2 may be a straight or branched chain alkyl group having 6 to 40 carbon atoms, more preferably 7 to 21, and most preferably 11 to 21. Preferred compounds include mono-, di- and tri-substituted sorbitans derived from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and mixtures thereof. Particularly preferred compounds include mono-, di- and tri-substituted sorbitan stearates, or sorbitan behenin.

[0077] In one embodiment, R α2 may contain at least one unsaturated bond. Examples of such compounds (wherein at least one active hydrogen substituent is -C(O)R α2 Selected from R α2 contains at least one unsaturated bond) includes sorbitan trioleate (i.e., in which R α2 H -C7H 14 CH=CHC8H 17 Other examples include, but are not limited to, mono-, di- and tri-substituted sorbitans derived from palmitoleic acid, linoleic acid, arachidonic acid and erucic acid.

[0078] In one aspect, the sorbitan modification (α21) has at least one active hydrogen substituent, the active hydrogen substituent being independently -(CH2CH2O) n (CH(CH3)CH2O) m R α2 or -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 (wherein each m is independently 0 to 20, each n is independently 0 to 20, and m+n is greater than 0). Such compounds are known as polysorbates and are commercially available under the trade name TWEEN. These sorbitans are also known as polysorbates. α2 Commercially available polysorbates can be mono-, di-, or trisubstituted with each R 2 From various polysorbates where R is H (unsubstituted), α2 It is known that sorbitan modifications (α21) contain a wide variety of mixtures ranging from polysorbates in which m is a linear or branched alkyl group having 6 to 40 carbons (fully substituted), and mixtures of these various substitutions. Examples of such sorbitan modifications (α21) include polysorbates such as polysorbate tristearate and polysorbate monostearate. m+n is greater than 0 and R α2Examples of sorbitan modifications (α21) containing at least one unsaturated bond include, but are not limited to, polysorbate trioleate (wherein R α2 is C7H 14 CH=CHC8H 17 and is commercially available under the name Polysorbate 80. Sorbitan modifications (α21) may include mixtures of compounds with various active hydrogen substituents, and R α2 A compound in which R contains at least one unsaturated bond. α2 may include mixtures with fully saturated compounds.

[0079] ((α22) citrate modified form) The sugar alcohol / hydroxy acid modified product (α2) may be a citric acid modified product (α22) in which citric acid is modified with a hydrocarbon group having 6 to 40 carbon atoms, in particular an alkyl citrate. For example, the citric acid modified product (α22) may exist as a mono-, di- or tri-substituted product with an alkyl group. The hydrocarbon group in the citric acid modified product (α22) may be the above-mentioned hydrocarbon group having 6 to 40 carbon atoms, and the above explanation is incorporated herein. The citric acid modified product (α22) may have an alkyl group having 12 to 30 carbon atoms. The above explanation is incorporated herein for the alkyl group having 12 to 30 carbon atoms. A mixture of citrates having various values ​​of active hydrogen substituents may also be used, and R α2 A compound having a hydrocarbon group having at least one unsaturated bond, and R α2 may include a mixture with a compound in which the citric acid modification (α22) is -(CH2CH2O) n (CH(CH3)CH2O) m R α2 or -(CHCHO) n (CH(CH3)CH2O) m C(O)R α2 wherein R α2 is a hydrocarbon group having 6 to 40 carbon atoms.) Examples of citric acid modifications (α22) include, but are not limited to, trialkyl citrates.

[0080] ((α23) Pentaerythritol modified) The sugar alcohol / hydroxy acid modified product (α21) may be a pentaerythritol modified product (α23) in which pentaerythritol is modified with a hydrocarbon group having 6 to 40 carbon atoms, or may be a mono-, di-, or tri-substituted product having a hydrocarbon group (particularly an alkyl group) having 6 to 40 carbon atoms, for example, a dipentaerythriol ester. The active hydrogen substituent is -CH2C[CH2OR α2 ]3, where R α2 is a hydrocarbon group having 6 to 40 carbon atoms). The pentaerythritol modification (α23) is a compound having a mixture of hydrocarbon groups with different chain lengths, or R α2 A compound in which R contains at least one unsaturated bond. α2 or a mixture of a compound in which the pentaerythritol modification (α23) is completely saturated with the pentaerythritol modification (α23). The hydrocarbon group in the pentaerythritol modification (α23) may be the above-mentioned hydrocarbon group having 6 to 40 carbon atoms, and the above explanation is incorporated herein. The pentaerythritol modification (α23) may have an alkyl group having 12 to 30 carbon atoms. The above explanation is incorporated herein for the alkyl group having 12 to 30 carbon atoms.

[0081] [(α3) Cationic active hydrogen compounds] The active hydrogen compound may be a cationic active hydrogen compound (α3) having an active hydrogen group and a cationic group.

[0082] Moreover, the cationic active hydrogen compound (α3) preferably has two or more hydroxy groups per molecule.

[0083] An example of the cationic group is a tertiary amino group.

[0084] That is, the cationic active hydrogen compound (α3) preferably has two or more hydroxyl groups per molecule as the active hydrogen groups, and a tertiary amino group as the cationic group.

[0085] Such cationic active hydrogen compounds can impart good dispersibility in a liquid medium (e.g., water) and can also introduce cationic groups having affinity for textile products (described later) into the resin, thereby improving washing durability.

[0086] More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as the active hydrogen groups, and a tertiary amino group as the cationic group.

[0087] Examples of such cationic active hydrogen compounds include alkyldialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, and propanolamine, and trialkanolamines such as N-triethanolamine and N-triisopropanolamine, and preferably N-methyldiethanolamine.

[0088] The cationic active hydrogen compound (or the portion in the non-fluorinated copolymer derived from the cationic active hydrogen compound) may form a salt with an acid compound.

[0089] Examples of the acid compound include organic acids and inorganic acids. Examples of the organic acid include acetic acid, lactic acid, tartaric acid, malic acid, and the like, preferably acetic acid and lactic acid, and more preferably acetic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, and the like, preferably hydrochloric acid. Examples of the acid compound include organic acids. If the acid compound contains an organic acid, the water repellency of the water repellent treated material treated with the water repellent composition can be improved by volatilizing the acid by heat treatment. In addition, the washing durability of the textile product can be improved from the viewpoint that the cationic group is easily adsorbed to the textile product by volatilizing the acid by heat treatment. [(α4) Other active hydrogen-containing compounds] The active hydrogen compound (α) may further contain an active hydrogen compound (α4).

[0090] ((α41) compound) The active hydrogen compound (α4) has the formula R α41 -X α41 [In the formula, In the formula, R α41 teeth, C1-C which may contain at least one unsaturated group 30 Straight or branched alkyl, hydroxy functional C1-C 30 Linear or branched alkyl, hydroxy-functional linear or branched C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy-functional linear or branched organosiloxanes, thiol-functional C1-C 30 Linear or branched alkyl, amine functional C1-C 30 Linear or branched alkyl, Y - R α411 R α412 R α413 N + -R α414 - (where Y is a halide ion, e.g., Cl - ), HOS(=O)2-R α414 - or R α411 R α412 C=N-(where R α411 , R α412 , R α413 are each independently -H or C1-C6 alkyl; R α414 is a divalent alkyl group having 1 to 20 carbon atoms; X α41 is -OH, -C(O)OH, -SH, -NH(R'), -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CHCHO) s (CH(CH3)CH2O) t -H, where R ’ is -H or a monovalent organic group, s is an integer from 0 to 50, t is an integer from 0 to 50, and s+t is greater than 0. It may be a compound (α41) represented by the following formula:

[0091] Compound (α41) may be a hydrophilic, water-soluble material comprising at least one hydroxy-terminated polyether, wherein X α41 is -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CH2CH2O)s(CH(CH3)CH2O) t -H. -(CH2CHO)- represents an oxyethylene group (EO) and -(CH(CH3)CHO)- represents an oxypropylene group (PO). These polyethers can contain only EO groups, only PO groups, or mixtures thereof. These polyethers may also exist as designated PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol) triblock copolymers.

[0092] In one embodiment, X α41 -OH, -C(O)OH, -SH, -NH(R ’ ) and R α41 C1-C optionally containing at least one unsaturated group 30 Straight or branched alkyl, hydroxy functional C1-C 30 Linear or branched alkyl, hydroxy-functional linear or branched C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy- or amine-functional linear or branched organosiloxanes, thiol-functional C1-C 30 Linear or branched alkyl, amine functional C1-C 30 It is selected from straight or branched chain alkyl.

[0093] X α41 may be -OH, and examples of such compounds (α41) include alkyl alcohols such as propanol, butanol, or fatty alcohols including stearyl alcohol (R α41 C1-C optionally containing at least one unsaturated group 30alkyl diols or polyols (R α41 is a hydroxyl functional group C1-C 30 alkylene glycol ethers such as triethylene glycol, tetraethylene glycol, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), or glycol ethers having a mixture of PEG, PPG or THF units (R α41 is a hydroxy-functional straight or branched chain C1-C 30 Polyether), polyester polyol (R α41 is a hydroxy-functional linear or branched polyester), silicone prepolymer polyol (R α41 is a hydroxy-functional linear or branched organosiloxane), N,N-dimethylaminoethanol (R α41 is an amine functional group C1-C 30 Straight or branched chain alkyl), choline chloride or betaine HCl (R α41 is Y - R α411 R α412 R α413 N + -R α414 -), butanone oxime (R α41 is R α411 R α412 C=N-). The polyether polyols can contain only EO groups, only PO groups, only THF groups, or mixtures thereof. These polyethers can also exist as block copolymers, such as those designated by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). The polyether glycols preferably have an average molecular weight of about 200 or more, most preferably 350 to 2000.

[0094] X α41may be -C(O)OH, and examples of such compounds (α41) include fatty acids (R 41 ) such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, linoleic acid, arachidonic acid, oleic acid, or erucic acid. α41 C1-C optionally containing at least one unsaturated group 30 straight or branched chain alkyl), hydroxy-containing acids such as hydroxycaprylic acid, hydroxycapric acid, hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyarachidic acid, hydroxybehenic acid, hydroxylignoceric acid, hydroxypalmitoleic acid, hydroxylinoleic acid, hydroxyarachidonic acid, hydroxyoleic acid, or hydroxyerucic acid (R α41 is a hydroxyl functional group C1-C 30 linear or branched alkyl), and mercaptoalkanoic acids such as mercaptopropionic acid (R α41 is a thiol functional group C1-C 30 Straight or branched chain alkyl).

[0095] X α41 may be -SH, and examples of such compounds (α41) include alkyl thiols (R α41 C1-C optionally containing at least one unsaturated group 30 Straight or branched chain alkyl).

[0096] X α41 may be -NH(R'), and examples of such compounds (α41) include alkylamines (R α41 C1-C optionally containing at least one unsaturated group 30 linear or branched alkyl), alkanolamines such as ethanolamine or propanolamine (R α41is a hydroxyl functional group C1-C 30 linear or branched alkyl), silicone prepolymer polyamine (R α41 is an amine-functional linear or branched organosiloxane), alkyl diamine (R α41 is an amine functional group C1-C 30 linear or branched alkyl), and aminoalkanesulfonic acids such as 2-aminoethanesulfonic acid (R α41 is HO-S(O)2R α414 -) are included, but are not limited to.

[0097] ((α42) compound) Compound (α42) has the formula R α421 -(OCH2CH(OR α422 )CH2) z -OR α423 [In the formula, R α421 , R α422 and R α423 At least one R α421 , R α422 or R α423 is -H, and each independently is -H, -R α424 , -C(O)R α424 and R α424 are independently a straight or branched alkyl group having 5 to 29 carbon atoms which may contain at least one unsaturated bond, and z is 1 to 15.

[0098] Compound (α42) may be a compound generally known as polyglycerol.Other specific examples include, but are not limited to, triglycerol monostearate, triglycerol distearate, hexaglycerol monostearate, hexaglycerol distearate, decaglyceryl mono(caprylate / caprate), decaglyceryl di(caprylate / caprate), decaglycerol, polyglycerol-3 and C18 diglyceride.

[0099] ((α43) Chain extender) The compound (α4) may be a chain extender (α43). The chain extender (α43) is a compound having two or more (for example, two) functional groups containing active hydrogen in the molecule. As the chain extender, a known chain extender can be used, and examples thereof include aliphatic or aromatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanedimethanol; aliphatic or aromatic diamines or polyamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, and diethyltoluenediamine; phenol hydroxyl group-containing compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol, and o,o'-diallyl-bisphenol A; and alcohol amines such as aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine, aminopropylpropanolamine, and aminohexylpropanolamine.

[0100] In one embodiment, the active hydrogen compound may be at least one selected from the group consisting of a hydrocarbon alcohol, a modified sugar alcohol, and a modified hydroxy acid.

[0101] [Raw isocyanate] The isocyanate derivative (B) has a moiety derived from the starting isocyanate.

[0102] The starting isocyanate may be an aromatic polyisocyanate, an acyclic aliphatic polyisocyanate, a cyclic alicyclic polyisocyanate, or a bridged cyclic alicyclic polyisocyanate.

[0103] Aromatic polyisocyanates are compounds having aromatic rings and isocyanate groups. The aromatic polyisocyanates may have one or more, two or more, or three or more aromatic rings, and may have five or less, four or less, or three or less aromatic rings.

[0104] The acyclic aliphatic polyisocyanate is an aliphatic polyisocyanate that does not have a ring structure. The acyclic aliphatic polyisocyanate may have an aliphatic hydrocarbon group having 2 to 20 carbon atoms. The aliphatic hydrocarbon group having 2 to 20 carbon atoms may be a divalent aliphatic hydrocarbon group. The carbon number of the aliphatic hydrocarbon group may be 2 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, or 14 or more, and preferably 4 or more, 6 or more, or 8 or more. The carbon number of the aliphatic hydrocarbon group may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, or 10 or less, and preferably 14 or less, 12 or less, or 10 or less. In one embodiment, the acyclic aliphatic polyisocyanate may be a polyisocyanate compound having an isocyanate group at the end of an alkylene group.

[0105] The cyclic alicyclic polyisocyanate is an aliphatic polyisocyanate having a ring structure. The cyclic alicyclic polyisocyanate has a carbon ring rather than an aromatic ring. The cyclic alicyclic polyisocyanate may have an aliphatic hydrocarbon group having 2 to 20 carbon atoms. The explanation of the aliphatic hydrocarbon group having 2 to 20 carbon atoms is incorporated in the above description of the acyclic aliphatic polyisocyanate.

[0106] The bridged cyclic alicyclic polyisocyanate is a polycyclic compound having a crosslinked structure in a ring structure by a methylene group or the like. The bridged cyclic alicyclic polyisocyanate may have an aliphatic hydrocarbon group having 2 to 20 carbon atoms. The explanation of the aliphatic hydrocarbon group having 2 to 20 carbon atoms is as described above for the acyclic aliphatic polyisocyanate.

[0107] The raw material isocyanate may be a derivative of the raw material isocyanate, for example, an isocyanurate derivative, an allophanate derivative, a polyol derivative, a biuret derivative, a urea derivative, an oxadiazinetrione derivative, a carbodiimide derivative, a uretdione derivative, a uretonimine derivative, or the like.

[0108] The starting isocyanate may be a derivative of a polyisocyanate selected from the group consisting of aromatic polyisocyanates, acyclic aliphatic polyisocyanates, cyclic alicyclic polyisocyanates, and bridged cyclic alicyclic polyisocyanates.

[0109] In one aspect, the starting isocyanate may be an isocyanurate or biuret derivative.

[0110] In one aspect, the starting isocyanate may be an acyclic aliphatic polyisocyanate.

[0111] Examples of raw material isocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or mixtures thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or mixtures thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4', or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixtures thereof) (XDI), tetramethyl xylylene diisocyanate (1,3- or aromatic polyisocyanates selected from 1,4-tetramethylxylylene diisocyanate or mixtures thereof (TMXDI), ω,ω'-diisocyanato-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4-, or 1,8-naphthalene diisocyanate or mixtures thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate; acyclic aliphatic polyisocyanates selected from trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaprate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate; 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylene bis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis(cyclohexyl isocyanate or mixtures thereof) (hydrogenated MDI), methylcyclohex cycloaliphatic polyisocyanates selected from sandiisocyanates (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrated TMXDI); a bridged cycloaliphatic polyisocyanate selected from norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanatomethyl bicycloheptane, and di(diisocyanatomethyl)tricyclodecane; [ka] [ka] A compound selected from: and biuret modified products of the above-mentioned isocyanates, polymers of polyisocyanates (for example, dimers, trimers (for example, isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), allophanate derivatives (for example, allophanate derivatives produced by the reaction of the above-mentioned polyisocyanates with monohydric alcohols or dihydric alcohols, etc.), polyol derivatives (for example, polyol derivatives (alcohol adducts, preferably trimethylolpropane) produced by the reaction of the above-mentioned polyisocyanates with trihydric alcohols (for example, trimethylolpropane, etc.) Examples of the polyisocyanate derivatives include dimethylaminopropylamine adducts (dimethylaminopropylamine adducts), biuret derivatives (for example, the biuret derivatives produced by the reaction of the above-mentioned polyisocyanates with water or amines), urea derivatives (for example, the urea derivatives produced by the reaction of the above-mentioned polyisocyanates with diamines), oxadiazinetrione derivatives (for example, the oxadiazinetriones produced by the reaction of the above-mentioned polyisocyanates with carbon dioxide), carbodiimide derivatives (for example, the carbodiimide derivatives produced by the decarboxylation condensation reaction of the above-mentioned polyisocyanates), uretdione derivatives, and uretonimine derivatives.

[0112] The average number of isocyanate groups in the raw material isocyanate is 2 or more, preferably 2.5, more preferably 2.9, and is, for example, 3.8 or less. The raw material isocyanate may be a polyisocyanate having a plurality of isocyanate groups.

[0113] [Method of synthesizing isocyanate derivative (B)]

[0114] To obtain the isocyanate derivative (B), the active hydrogen compound is reacted with the raw material isocyanate. The reaction may be carried out in one step, or may be carried out successively in multiple steps. For example, when the product contains unreacted active hydrogen groups or active hydrogen reactive groups, the synthesis may be carried out successively. The successive reaction is particularly useful when using a substituted sugar alcohol having a high OH number. The reaction conditions, such as the reaction concentration and reaction temperature, are not particularly limited and can be determined by a person skilled in the art. Specifically, the active hydrogen compound and the raw material isocyanate may be blended so that the equivalent ratio of the active hydrogen reactive group (isocyanate group) to the active hydrogen group (active hydrogen reactive group / active hydrogen group) is, for example, 1.2 or more, preferably 1.5 or more, and, for example, 2.0 or less.

[0115] [Composition of isocyanate derivative] The amount of the portion derived from compound (α) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, based on the isocyanate derivative (B). The amount of the portion derived from monomer (α) may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, based on the isocyanate derivative (B).

[0116] The amount of the portion derived from the hydrocarbon alcohol (α1) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, based on the portion derived from the active hydrogen compound. The amount of the portion derived from the hydrocarbon alcohol (α1) may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, relative to the portion derived from the active hydrogen compound.

[0117] The amount of the portion derived from the sugar alcohol / hydroxy acid modified product (α2) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more relative to the portion derived from the active hydrogen compound. The amount of moieties derived from sugar alcohol / hydroxy acid modifications may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less relative to the moieties derived from active hydrogen compounds.

[0118] The amount of the portion derived from the cationic active hydrogen compound (α3) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, based on the portion derived from the active hydrogen compound. The amount of the portion derived from the cationic active hydrogen compound (α3) may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, based on the portion derived from the active hydrogen compound.

[0119] The amount of the portion derived from the other active hydrogen-containing compound (α4) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more relative to the portion derived from the other active hydrogen-containing compound (α4). The amount of the portion derived from the other active hydrogen-containing compound (α4) may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, relative to the portion derived from the active hydrogen compound.

[0120] The amount of the portion derived from the raw material isocyanate may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, based on the isocyanate derivative (B). The amount of the portion derived from the raw isocyanate may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, based on the isocyanate derivative (B).

[0121] [Amount of isocyanate derivative (B)] The amount of the isocyanate derivative (B) 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, per 100 parts by weight of the non-fluorinated copolymer (A). The amount of the isocyanate derivative (B) 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, per 100 parts by weight of the non-fluorinated copolymer (A).

[0122] 〔silicone〕 The water repellent composition of the present disclosure preferably contains silicone in addition to the hydrophobic monomer (a1), which can provide good water repellency and slip resistance.

[0123] Silicones have the formula: (R 53 )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:

[0124] 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, 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.

[0125] 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 R 51At least one of (for example, one of) 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, preferably 10 or more or 23 or more. Here, the hydrocarbon group may be linear or branched, and is preferably an alkyl group. Specific examples of the hydrocarbon group 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).

[0126] The long-chain hydrocarbon group R 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.

[0127] 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.

[0128] 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.

[0129] When a or b is 2 or more, R exists in plural. 51 and R 52 Each of may be the same or different.

[0130] R51 and R 53 Group (for example, R 51 and R 52 Groups and R 53 It is preferable that 50 mol % or more of the total of the alkyl groups) are methyl groups.

[0131] The order of the repeating units bounded by a or b is not limited to the order shown in the chemical formula, but may be any order, i.e., the silicone may be a random polymer or a block polymer.

[0132] 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 53 may 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.

[0133] 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; and n is an integer from 1 to 36 (preferably, n is a long-chain hydrocarbon group).

[0134] Silicone can be synthesized by a conventional method, for example, by subjecting silicone having a SiH group to a hydrosilylation reaction with an α-olefin.

[0135] Examples of silicones having a SiH group include methylhydrogensilicones having a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methylhydrogensiloxane. Among these, methylhydrogensilicones are preferred because they are easy to produce industrially and obtain. Hydrogensilicones (e.g., methylhydrogensilicones) are polydiorganosiloxanes in which a portion of the side chain is replaced with hydrogen, and the hydrogen atom is directly bonded to a silicon atom. 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. As these catalysts, organic acid metal salts are preferred, and as organic acids, fatty acids are preferred. From the viewpoint of excellent handling, zinc stearate or the like can be used. It is preferable to use 10 to 40% of the catalyst relative to the methylhydrogensilicone, since the catalyst is more likely to exert its effect. Two or more of amino-modified, epoxy-modified, carboxy-modified, and methylhydrogensilicones may be mixed. All of them are silicones having reactive groups, and it is preferable that they are silicones having 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 it is attached to the fiber surface in an emulsion state.

[0136] α-Olefins are compounds from which long-chain hydrocarbon groups in silicones are derived. Specific examples of α-olefins are 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 a SiH group with an α-olefin in a stepwise manner or all at once, if necessary in the presence of a catalyst.

[0137] 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 or number average molecular weight of the SiH group-containing silicone, respectively.

[0138] Examples of catalysts used in the hydrosilylation reaction include platinum and palladium compounds, and among these, platinum compounds are preferred, such as platinum(IV) chloride.

[0139] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be appropriately adjusted. The reaction temperature is, for example, 10 to 200° C., and 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 the inert gas include nitrogen and argon. The reaction proceeds without a solvent, but a solvent may be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0140] (Reactive Silicone) The silicone may include reactive silicone. Examples of reactive silicone include polysiloxanes having reactive groups at the side chain, one end, both ends, or at the side chain and both ends. From the viewpoint of excellent slip resistance and excellent water repellency at the same time, polysiloxanes having reactive groups at the side chain and / or both ends may be used. The reactive silicone is not particularly limited as long as it has a reactive group in the molecule, and examples thereof 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) are replaced with reactive groups.

[0141] The amino-modified silicone may have 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 is preferably one having 2 or more carbon atoms. The divalent aromatic group is preferably one having 6 or more carbon atoms. The amino group may be either a primary amino group, a secondary amino group, or a tertiary amino group. Examples of organic groups bonded to an amino group 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-anopropyl 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 ends.

[0142] The epoxy-modified silicone may have 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. In this case, the bond between the organic group and the epoxy group is usually in the form of a glycidyl ether. Examples of such functional groups include a 3-glycidoxypropyl group and a 2-glycidoxyethyl group. These functional groups may be in the side chain of the polysiloxane or at the end.

[0143] 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 is preferably one having 2 or more carbon atoms. The divalent aromatic group is preferably one having 6 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 in the side chain of the polysiloxane or at the terminal.

[0144] (Silicone resin) The silicone may include a silicone resin. The silicone resin may include RSiO 1 / 2 Unit (M unit), RSiO 3 / 2 Units (T units) and SiO 4 / 2 The silicone resin (B) 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 from the viewpoint of exerting the effect of the present invention.

[0145] 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, but from the standpoint of stability when silicone resin (B) is in a sol state, availability of raw materials, and price, R is preferably a methyl group, and more than 90% of all R are preferably methyl groups. Note that R may be used in combination with different types of groups.

[0146] Silicone resin with R2SiO 2 / 2 If the silicone resin contains D units, the anti-skid properties of the water repellent composition may be impaired, and if the silicone resin contains only Q units, the water repellent properties of the water repellent composition may be impaired.

[0147] The structure of the silicone resin is exemplified by (i) 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, and preferably (i) silicone resins consisting of M units and Q units and (v) silicone resins consisting only of T units. (i) The molar ratio (M / Q) of M units and Q units of the silicone resin consisting of M units and Q units is preferably M / Q=0.6 to 1.3, more preferably M / Q=0.8 to 1.1. Two or more of these silicone resins may be used in combination.

[0148] The silicone resin (B) 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 A part of the hydroxyl groups may be an alkoxy group represented by an RO group.

[0149] As described in Japanese Patent No. 3852921, a sol containing a silicone resin 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 compound is hydrolyzed in water.

[0150] The production method of hydrolyzing a silane compound in water will be described in detail. As a raw material for production, any silane compound can be used as long as the type of 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, dimethylcetyl chlorosilane, dimethylcetyl methoxysilane, dimethylcetyl 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.

[0151] As a method for hydrolyzing a silane compound in water, a commonly known method can be used, such as a method in which the hydrolysis reaction is carried out while dropping the silane compound 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. As the hydrolysis catalyst, a conventionally known catalyst may be used, and it is preferable to use an acidic or alkaline one. In the case of an acidic catalyst, a solid acid such as hydrogen halide, carboxylic acid, sulfonic acid, acidic or weakly acidic inorganic salt, or ion exchange resin is preferable. In the case of an alkaline catalyst, an alkali metal salt such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or sodium hydrogen carbonate, an alkali metal silanolate such as sodium silanolate or potassium silanolate, an amine such as triethylamine, diethylamine, or aniline, or an aqueous ammonia may be used. The amount of the catalyst to be added is preferably adjusted so that the pH of the aqueous solution is 2 to 7 or 7 to 12. After the reaction is completed, a neutralizing agent for neutralizing the acidic or alkaline catalyst may be added as necessary.

[0152] A surfactant may be added to the aqueous solution in order to disperse the silane compound and the hydrolysis reaction product in water. There is no particular limitation on the surfactant, but for example, 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 can be used alone or in combination of two or more. In addition, surfactants that exhibit acidity or alkalinity can also be used as hydrolysis catalysts. There is no particular limitation on the amount of surfactant added, but it is preferably 1 to 50 parts by weight per 100 parts by weight of the silane compound. If the amount is less than 1 part by weight, the effect of adding the surfactant is not sufficiently obtained, and if the amount is more than 50 parts by weight, the water repellency of the water repellent agent may be impaired.

[0153] A hydrolysis catalyst and a surfactant may be added to the mixture of water and the silane compound as necessary, and the hydrolysis reaction may be carried out at 0 to 90°C for 10 minutes to 24 hours. Silicone resin can be obtained by subsequently carrying out a neutralization reaction as necessary. In addition, alcohols and neutralized salts produced as by-products in the hydrolysis reaction can be removed by vacuum distillation, filtration, or the like. Various additives can be added to this silicone resin. For example, preservatives, thickeners, and the like can be added depending on the purpose.

[0154] (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 non-fluorinated copolymer (A). 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 non-fluorinated copolymer (A).

[0155] 〔wax〕 The water repellent composition of the present disclosure preferably contains a wax in addition to the hydrophobic monomer (a1). By containing a wax, water repellency and slip resistance can be well combined. The water repellent composition of the present disclosure may contain both silicone and wax, or may contain only one of silicone and wax.

[0156] Examples of wax 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 wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, 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, 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.

[0157] 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.

[0158] (amount of wax) The amount of the wax may be 0.1 part 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 non-fluorinated copolymer (A). The amount of the wax 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 non-fluorinated copolymer (A).

[0159] [Inorganic particles] The water repellent composition of the present disclosure may contain inorganic particles. By containing inorganic particles, water repellency and slip resistance can be better imparted. The inorganic particles may be an aluminum compound (e.g., alumina), a silicon compound (e.g., silica), a titanium compound, 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.

[0160] 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, and is preferably 40 nm or less. By being in the above range, water repellency and slip resistance can be well combined. The average primary particle diameter can be measured with a microscope (scanning electron microscope or transmission electron microscope). Specifically, an arbitrary position of the fabric is observed from above with an arbitrary magnification using a microscope. Next, when the particle shape is spherical, the diameter is regarded as the particle diameter (particle diameter), and when it is non-spherical, the average value of the longest diameter and the shortest diameter is regarded as the particle diameter (particle diameter). The particle size of all particles present within 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 the particle sizes are measured at 10 or more points, and the average value is the average primary particle size.

[0161] (Amount of inorganic particles) The amount of the inorganic particles 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 non-fluorinated copolymer (A). The amount of the inorganic particles 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 non-fluorinated copolymer (A).

[0162] [Liquid medium] The water repellent composition may contain a liquid medium. The liquid medium is water, an organic solvent, or a mixture of water and an organic solvent. A mixture of water and an organic solvent is preferable. By containing an organic solvent, the water repellency and slip resistance can be well combined.

[0163] Examples of the organic solvent include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, 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, kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxyl group (e.g., polyhydric alcohols such as alcohols, glycol-based solvents, ethers of polyhydric alcohols (e.g., monoethers), etc.). These may be used alone or in combination of two or more.

[0164] (amount of liquid medium) The amount of the liquid medium may be 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 97% by weight or more, based on the water repellent composition. The amount of the liquid medium may be 99.9% by weight or less, 99% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, or 50% by weight or less, based on the water repellent composition.

[0165] The amount of the organic solvent may be 0.5% by weight or more, 1% by weight or more, 2% by weight or more, 3% by weight or more, 5% by weight or more, 7.5% by weight or more, 10% by weight or more, 12.5% ​​by weight or more, 15% by weight or more, or 20% by weight or more, based on the water repellent composition. The amount of the organic solvent may be 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 25% 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 water repellent composition.

[0166] 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 liquid medium. The amount of the organic solvent may be 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 liquid medium.

[0167] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, relative to 100 parts by weight of the non-fluorinated copolymer (A). The amount of the organic solvent may be 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 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 non-fluorinated copolymer (A).

[0168] The amount of the organic solvent may be 0.5 parts by weight or more, 1 part by weight or more, 1.5 parts 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, 20 parts by weight or more, 30 parts by weight or more, or 40 parts by weight or more, based on 100 parts by weight of water. The amount of the organic solvent may be 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 25 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, based on 100 parts by weight of water.

[0169] [Dispersant] The water repellent composition may contain a dispersant to enhance the dispersibility of the non-fluorinated copolymer (A). The dispersant may be a polymer dispersant, preferably a hydrophilic polymer dispersant. As the dispersant, polyvinylpyrrolidone, polyvinyl alcohol, polyglycerin, polyacrylate, etc. may be used. These may be used alone or in combination of two or more.

[0170] (amount of dispersant) The amount of the dispersant may be 0.1 part 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 non-fluorinated copolymer (A). The amount of the dispersant 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 non-fluorinated copolymer (A).

[0171] [Surfactant] The water repellent composition preferably contains a surfactant. In the water repellent composition, the surfactant may contain a nonionic surfactant. By containing a surfactant, water repellency and slip resistance can be well combined. Furthermore, the surfactant may contain one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant.

[0172] (Nonionic surfactant) Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides.

[0173] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0174] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a monohydric to hexahydric (particularly dihydric to pentahydric) alcohol (e.g., an 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.

[0175] An example of the 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 the alcohol is a monohydric to hexahydric (particularly dihydric to pentahydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 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.

[0176] 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, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0177] The polyhydric alcohol may be a dihydric to pentahydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (eg, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0178] 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.

[0179] 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 portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Moreover, the nonionic surfactant preferably has a structure that does not contain an aromatic group in view of environmental issues (biodegradability, environmental hormones, etc.).

[0180] The nonionic surfactant has 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 each is independently the same or different and is an alkylene group 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 a number equal to or greater than 2, q is a number equal to or greater than 0. The compound may be represented by the formula:

[0181] R1 R preferably has 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms. 1 Preferred specific examples include a lauryl group, a tridecyl group, and an oleyl group. R 2 Examples are 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) in 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.

[0182] 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.

[0183] The proportion of the polyoxyethylene block may be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight, 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.

[0184] (Cationic Surfactant) The cationic surfactant is preferably a compound having no amide group.

[0185] 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, imidazoline, etc., alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, pyridinium salts, alkyl isoquinolinium salts, and quaternary ammonium salt surfactants such as benzethonium chloride.

[0186] Preferred examples of the cationic surfactant are: R 21 -N + (-R 22 )(-R 23 )(-R 24 ) X - [In the formula, R 21 , R 22 , R 23 and R 24 is a hydrocarbon group having 1 to 40 carbon atoms, X is an anionic group. It is a compound of the formula: R 21 , R 22 , R 23and -R 24 Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0187] The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula: R 1 p - N + R 2 q X - [In the formula, R 1 is C12 or higher (e.g. C 12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50); (CH3, 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 1 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0188] 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.

[0189] 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 fatty acid salts, N-acylamino acid type surfactants, phosphoric acid mono- or diester type surfactants, and sulfosuccinic acid esters.

[0190] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amido betaines, and betaine acetate. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetate betaine, and fatty acid amidopropyl dimethylamino acetate betaine.

[0191] 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.

[0192] (amount of surfactant) The amount of the surfactant may be 0.1 part 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 non-fluorinated copolymer (A). The amount of the surfactant 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 non-fluorinated copolymer (A). The amount of the cationic surfactant may be 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more, based on the total amount of the surfactants. The weight ratio of the nonionic surfactant to the cationic surfactant is preferably 95:5 to 20:80, more preferably 85:15 to 40:60. The amount of the cationic surfactant may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight, relative to 100 parts by weight of the water-repellent resin. The total amount of the surfactants may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight, relative to 100 parts by weight of the water-repellent resin.

[0193] [Hardening agent] The water repellent composition may contain a curing agent (an active hydrogen reactive compound or an active hydrogen-containing compound). After the polymerization to obtain the non-fluorinated copolymer (A), the curing agent may be added to the water repellent composition.

[0194] The curing agent (crosslinking agent) in the water repellent composition can satisfactorily cure the non-fluorine copolymer (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 non-fluorine copolymer (A). Examples of the active hydrogen reactive compound are polyisocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds and hydrazide compounds. Examples of the active hydrogen-containing compound are hydroxyl group-containing compounds, amino group-containing compounds and carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds and melamine compounds.

[0195] The curing agent may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates.

[0196] 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, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-di ... Aliphatic diisocyanates such as cyanatomethyl 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, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, etc. These may be used alone or in combination of two or more.

[0197] 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.

[0198] Examples of the araliphatic polyisocyanate are araliphatic diisocyanate and araliphatic triisocyanate.Specific examples of the araliphatic polyisocyanate are 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.

[0199] Examples of aromatic polyisocyanates are aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates are 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.

[0200] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdione, uretoimine, isocyanurates, iminooxadiazinedione, etc. These may be used alone or in combination of two or more.

[0201] These polyisocyanates can be used alone or in combination of two or more. 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. It is preferable to use a blocked polyisocyanate compound because it is relatively stable even in an aqueous solution and can be used in the same aqueous solution as the water repellent composition.

[0202] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, for example, 130°C or higher, the isocyanate group is regenerated and can easily react with the hydroxyl group. Examples of the blocking agent include phenol-based compounds, lactam-based compounds, aliphatic alcohol-based compounds, and oxime-based compounds. The polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0203] 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. The chloromethyl group-containing compound is a compound having a chloromethyl group. An example of the chloromethyl group-containing compound is chloromethyl polystyrene. 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.

[0204] Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide, and the like. Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0205] (Amount of hardener) The amount of the curing agent may be 0.1 part 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 non-fluorinated copolymer (A). The amount of the curing agent 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 non-fluorinated copolymer (A).

[0206] The above-mentioned silicone, wax, inorganic particles, liquid medium, dispersant, surfactant or curing agent may be added after the production of the fluorine-free copolymer (A), or the fluorine-free copolymer (A) may be produced by polymerizing the monomers for the fluorine-free copolymer (A) in the presence of the above-mentioned silicone, wax, inorganic particles, liquid medium, dispersant, surfactant or curing agent.

[0207] [Other ingredients] The water repellent composition may contain other components in addition to the above components. After producing the non-fluorinated copolymer (A), other components may be added. Examples of other components include water and / or oil repellents, antislip agents, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above ingredients, other ingredients include texture adjusters, fabric softeners, antibacterial agents, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming agents, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrink prevention agents, laundry wrinkle prevention agents, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Chinopearl CBS-X), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, and stain removers. As fiber surface modifiers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc., foam inhibitors, moisture absorption and release properties, etc., can be used to impart silk texture and functions, such as silk protein powder, surface modified products thereof, and emulsified dispersions. Specifically, K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemicals), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos), non-ionic polymer compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units, such as FR627 manufactured by GOO Chemical Industry Co., Ltd. and SRC-1 manufactured by Clariant Japan, and other stain prevention agents can be blended. These may be used alone or in combination of two or more.

[0208] (Antistatic agent) Examples of the antistatic agent 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, sulfates, phosphonates, and phosphates; amphoteric antistatic agents such as alkylbetaines and their derivatives, imidazolines and their derivatives, alanines and their derivatives, nonionic antistatic agents such as aminoalcohols and their derivatives, glycerin and its derivatives, and polyethylene glycols and its derivatives. The antistatic agent may be an ion-conductive polymer obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ion-conductive groups. These may be used alone or in combination of two or more.

[0209] (Antibacterial and antifungal agent) The antibacterial and antifungal agent is at least one type of antibacterial and antifungal agent that inhibits the growth of microorganisms such as bacteria, preferably both fungi and bacteria. The antibacterial and antifungal agent is not particularly limited, but the following commonly used antibacterial and antifungal agents listed in the Journal of the Japanese Society of Antibacterial and Antifungal Agents, Vol. 26, 1998, can be used.

[0210] Amines such as Bis(3-aminopropyl)dodecylamine (trialkyltriamine), Alcohols such as Ethyl alcohol (Ethanol), Isopropyl alcohol (Isopropanol), Propyl alcohol (Propanol), Tris (hydroxymethyl) nitromethane (Trisnitro), 1,1,1-Trichloro-2-methyl-2-propanol (Chlorobutanol), 2-Bromo-2-nitropropane-1,3-diol (Pronobol, Pronosol, Pronocot), Aldehydes such as 1,5-Pentanediol (glutaraldehyde), formaldehyde, and α-bromocinnamic aldehyde, Isothiazolinones such as 2-n-Octyl-4-isothiazolin-3-one (Skein M-8), 5-Chloro-2-methyl-4-isothiazolin-3-one / 2-Methyl-4-isothiazolin-3-one (Caisson CG, NS-500W), 1,2-Benzisothiazolone-3 (BIT), and Nn-Butyl-1,2-benzisothiazolone-3 (n-Butyl BIT), Isothiocyanates such as allyl isothiocyanate, Imidazoles such as 2-(4-Thiazolyl)-benzimidazol (TBZ) and Methyl-2-benzimidazole carbamate (Preventol BCM), Esters such as glycerol laurate (lauricidin, glyceryl monolaurate, monoglyceride), Oxazolidines such as 4,4-Dimethyl-1,3-oxazolidine (Biopan CS-1135, Oxazin A) Carbanilides such as 3,4,4'-Trichlorocarbanilide (triclocarban, trichlorocarbanilide) and 4,4'-Dichloro-3-(3-Fluoromethyl)-carbanilide (halocarban, cloflucarban), Carbamate series such as 3-iodo-2-propynylbutyl carbamate (Glycical), Carboxylic acids such as Benzoic acid, Flexa-2,4-dienoic acid, 2-propanylacrylic acid, Octanoic acid, Propionic acid, Undecylenic acid, Potassium hexa-2,4-dienoic acid, Potassium propionate, Calcium propionate, Sodium benzoate, Sodium propionate, Magnesate(2-),bis(2-carboxybenzene carboperoxato)dihydrogene, Zinc undecylenate, etc. Quinoline-based compounds such as 8-hydroxyquinoline, Bis(quinolin-8-olate)copper (quinoline copper, oxine copper, 8-quinolinol copper), Sulfide-based compounds such as Bis(dimethylthiocarbamoyl)disulfide (TMTD, thiuram), Diphenyl ethers such as 2,4,4'-Trichloro-2'-hydroxydiphenyl (Triclosan, Irgasan DP300), Sulfamides such as N,N-Dimethyl-N'-(fluorodichloromethylthio)-N"-phenylsulfamide (Cyclofluanid, Preventol A4-S) and N-Dichlorofluoromethylthio-N',N'-dimethyl-Np-torylsulfamide (Trifluanid, Preventol A5) Proteins such as Protamine (milt protein, milt hydrolysate, nuclear protein) and Hen egg lysozyme (egg white lysozyme) Thiazoles such as 2-(4-Thiocyanomethylthio)benzothiazol, Thiocarbamate such as sodium N-methyldithiocarbamate (sodium N-methyldithiocarbamate, sodium carbamate) Hexahydro-1,3,5-tris(hydroxyethyl)-S-triadine (Biopan GK, triazine), Triazines such as CAVINON(100,200) and α-[2-(4-chlorophenyl)ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol (devconazole), Tropolones such as 4-Isopropyl-2-hydroxy-cyclohepta-2,4,6-triene-1-one (hinokitiol, β-thujaplicin), Nitriles such as 2,4,5,6-Tetrachloroisophthalonitrile and 1,2-Dibromo-2,4-dicyanobutane (Tectormal 38), Biguanides such as 1,1'-(Hexamethylene bis[5-(4-chlorophenyl)biguanide]digluconate and Bis(p-chlorophenyldiguanide)hexane dihydrochloride, Hydantoin derivatives such as 1-Bromo-3-chloro-5,5'-dimethyl hydantoin (Dantobrom) and 1,3-Bis-(hydroxymethyl)-5,5'-dimethyl hydantoin (Glydant, Dantoguard), Pyridine-based compounds such as sodium pyridine thiol-1-oxide (sodium pyrithione), zinc bis(2-pyridylthio-1-oxide) (zinc pyrithione, zinc omadine, ZPT), 2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine (densil), and copper bis(2-pyridylthio-1-oxide) (copper pyrithione, copper omadine, CuPT), 2-Isopropyl-5-methylphenol (thymol, 2-isopropyl-5-methylphenol), 3-Methyl-4-isopropylphenol (isopropylmethylphenol, piosol), o-Phenylphenol (OPP, orthophenylphenol), Phenol (phenol, carbolic acid), Butyl-p-hydroxybenzoate (butylparaben), Ethyl-p-hydroxybenzoate (ethylparaben), Methyl-p-hydroxybenzoate (methylparaben), Propyl-p-hydroxybenzoat Phenols such as e (propylparaben), m-Methylphenol (metacresol), o-Methylphenol (orthocresol), p-Methylphenol (paracresol), o-Phenylsodiumphenoxide (sodium orthophenylphenol), 2-Benzyl-4-chlorophenol (chlorophene), p-Chlorophenol (parachlorophenol), 4-Chloro-3,5-dimethylphenol (parachlorometaxylenol), and 2-Methyl-3-chlorophenol (parachlorometacresol), Phthalimide-based compounds such as N-(Fluorodichloromethylthio)-phthalimide (Fluorofolpet, Briventol A3), Peptide systems such as ε-Poly-L-lysine (ε-polylysine), Morpholine derivatives such as 4-(2-nitrobutyl)morpholine / 4,4'-(2-nitrotrimethylene)dimorpholine (Biopan P-1487) Iodine-based compounds such as Diiodomethyl-p-trylsulfone, Polyvinylpyrolidone iodide, p-Chlorophenyl-3-iodopropagyl formal, and 3-Bromo-2,3-diiodo-2-propenylethylcarbonate (Sunplus), Chlorine-based substances such as sodium hypochlorite, sodium dichlorinated isocyanurate, and trichlorinated isocyanuric acid, Peroxides such as hydrogen peroxide, chlorine dioxide (stabilized chlorine dioxide, Biotalk), and peracetic acid. Metal salts such as copper naphthenate, silver / zirconia phosphate (Novaron AG300), silver chloride / titanium oxide, silver-zinc / calcium phosphate (Silver Ace), silver-zinc / zeolite (silver zinc aluminosilicate, silver zinc zeolite), zinc oxide, silver / zirconia phosphate (Novaron AGZ330), and N-stearoyl-L-glutamic acid AgCu salt (Holon Killer), Antibiotics such as 1-L-(1,3,5 / 2,4)-1,5-Diamino-4-O-(2,5-dideoxy-α-D-glucopyranosyl)-2,3-cyclohexandiol (ST-7), Oxides such as ethylene oxide (EO) and propylene oxide (PO), 4,4'-(Tetramethylenedicarbonyldiamino)bis(1-decylpyridinium bromide)(dimer 135), Decyldimethylbenzylammonium chloride, Didecyldimethylammonium chloride (Didecyldimethylammonium chloride, Bardac 2250 / 80), Diisobutylphenoxyethoxydimethylbenzylammonium chloride (Benzotonium chloride, Hyamine 1622), Hexadecyl trimethyl ammonium bromide (Cetylammonium bromide, Cetrimide, CTAB, Sekubron), N,N'-Hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide)(dimer 38), N-Alkyl-N,N-dimethyl-N-benzylammonium chloride (Benzalkonium chloride, Hyamine 3500J), N-Decyl-N-isononyl-N,N'-dimethylammonium quaternary ammonium salts such as hexadecyl pyridinium chloride (cetylpyridinium chloride), 5-(trimethoxysilyl)propyldimethyloctadecylammonium (DC-5700), and hexadecyl pyridinium chloride (cetylpyridinium chloride), Carbohydrates such as β-1,4-Poly-D-glucosamine (chitosan), Examples include urea-based agents such as N'-(3,4-dichlorophenyl)-N,N-dimethylurea (Duuron, DCMU, Briventol A6). In particular, isothiazoline-based antibacterial and antifungal agents such as 2-n-octyl-4-isothiazolin-3-one (Skein M6), a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one (BIT), and Nn-butyl-1,2-benzisothiazolin-3-one (BBIT) are preferred.

[0211] In particular, isothiazoline-based antibacterial and antifungal agents such as 2-n-octyl-4-isothiazolin-3-one, a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one (BIT), Nn-butyl-1,2-benzisothiazolin-3-one (BBIT), etc. These antibacterial and antifungal agents can be used alone or in combination of two or more.

[0212] The amount of the antibacterial and antifungal agent may be 1.5 ppm or more, 7.5 ppm or more, 30 ppm or more, 75 ppm or more, or 100 ppm or more as an active ingredient concentration relative to the entire water repellent composition, and may be 600 ppm or less, 450 ppm or less, 300 ppm or less, 200 ppm or less, 150 ppm or less, or 100 ppm or less. For example, the amount of the antibacterial and antifungal agent may be 1.5 to 450 ppm, preferably 7.5 to 300 ppm, particularly preferably 75 to 150 ppm, relative to the entire water repellent composition.

[0213] The amount of the antibacterial and antifungal agent may be 1.5 ppm or more, 7.5 ppm or more, 30 ppm or more, 75 ppm or more, 150 ppm or more, 250 ppm or more, or 300 ppm or more, and may be 1500 ppm or less, 1000 ppm or less, 750 ppm or less, 450 ppm or less, 300 ppm or less, 200 ppm or less, 150 ppm or less, or 150 ppm or less, relative to the non-fluorine copolymer (A). For example, the amount of the antibacterial and antifungal agent may be 4.5 to 1350 ppm, preferably 22.5 to 900 ppm, particularly preferably 225 to 450 ppm, relative to the non-fluorine copolymer (A).

[0214] The antibacterial and antifungal agent may be used as a preservative or antibacterial agent for the following:

[0215] (Preservatives) The preservative can be used mainly to enhance the preservative power and the bactericidal power and to maintain the preservative property during long-term storage. For example, isothiazolinone-based organic sulfur compounds, benzisothiazoline-based organic sulfur compounds, benzoic acids, 2-Bromo-2-nitropropane-1,3-diol, etc. The amount of the preservative is preferably 0.0001 to 1% by weight based on the total weight of the water repellent composition. When the amount of the preservative is equal to or more 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.

[0216] (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 resulting from the decomposition products of microorganisms. Examples of antibacterial agents include cationic bactericides such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, polylysine, etc.

[0217] (UV absorber) An ultraviolet absorber is a drug that has an ultraviolet protection effect, and is a component that absorbs ultraviolet light and converts it into infrared light, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, 4-t-butyl-4'-methoxybenzoylmethane, etc.

[0218] (Deodorant) Examples of deodorants include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (zinc complex of trisodium methylglycinediacetate described in WO 2012 / 090580).

[0219] (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", Indo Genichi, Kagaku Kogyo Nipposha (1996); "Perfume and Flavor Materials of Natural Origin", Steffen Arctander, Allured Pub. Co. (1994); "Encyclopedia of Fragrance", edited by the Japan Fragrance Manufacturers Association, Asakura Shoten (1989); "Perfumery Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996); and "Flower oils and Floral Compounds In Perfumery", Danute Lajaujis Anonis, Allured Pub. Co. (1993), each of which is incorporated herein by reference.

[0220] (Amount of other ingredients) The amount of the other components 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 non-fluorinated copolymer (A). The amount of the other components 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 non-fluorinated copolymer (A).

[0221] <Method of producing water repellent composition> The method for producing the water repellent composition includes copolymerizing a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms with at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride in the presence of an isocyanate derivative (B) to obtain a non-fluorinated copolymer (A). By this method (hereinafter referred to as the first method), the water repellent composition of the present disclosure can be obtained.

[0222] In one embodiment, the method for producing the water repellent composition includes copolymerizing a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms with at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride in the presence of an isocyanate derivative (B), a surfactant, and a liquid medium to obtain a non-fluorinated copolymer (A). By such a method, the water repellent composition of the present disclosure can be obtained.

[0223] Examples of the polymerization method include suspension polymerization and emulsion polymerization, and from the viewpoint of obtaining an emulsion of the non-fluorinated copolymer (A), emulsion polymerization is used.

[0224] When emulsion polymerization is employed, first, all or a part of the above-mentioned monomers (specifically, hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms, at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride, cyclic hydrocarbon group-containing monomer (a3) ​​which is blended as necessary, crosslinkable monomer (a4) which is blended as necessary, and other monomers (a5) which are blended as necessary) are mixed with an isocyanate derivative (B), a surfactant, and a liquid medium to prepare a mixed liquid.

[0225] The surfactant may be added in an amount of, for example, 1 part by weight or more, preferably 3 parts by weight or more, and for example, 10 parts by weight or less, preferably 5 parts by weight or less, relative to 100 parts by weight of the total amount of the monomers (specifically, the hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms, at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride, the cyclic hydrocarbon group-containing monomer (a3) ​​which is added as necessary, the crosslinkable monomer (a4) which is added as necessary, and other monomers (a5) which are added as necessary, hereinafter the same).

[0226] The blending ratio of the liquid medium may be, for example, 100 parts by weight or more, preferably 200 parts by weight or more, and for example, 400 parts by weight or less, preferably 300 parts by weight or less, relative to 100 parts by weight of the total amount of the monomers. 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 be further added. The organic solvent may be any of those listed above. The organic solvent may be a water-soluble glycol solvent, for example, ethylene glycol or propylene glycol.

[0227] In the 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 weight or more, 0.1 parts by weight or more, 1 part by weight or less, 0.5 parts by weight or less, based on 100 parts by weight of the total amount of the monomers.

[0228] An emulsifier may then be added to this mixture.

[0229] The emulsifier may be any known emulsifier, such as a cationic emulsifier or an anionic emulsifier.

[0230] As the emulsifier, the above-mentioned surfactants can also be used.

[0231] The emulsifier may contain a reactive emulsifier. When the emulsifier contains a reactive emulsifier, the non-fluorinated copolymer (A) (polymer of the above monomer) becomes a polymer containing structural units derived from the reactive emulsifier.

[0232] When the non-fluorinated copolymer (A) is a polymer containing a structural unit derived from a reactive emulsifier, the product stability of the aqueous dispersion (repellent composition) is improved without decreasing the water repellency.

[0233] 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 the reactive emulsifier include the reactive emulsifiers described in JP 2017-25440 A, and preferably the reactive emulsifier represented by the following formula: [ka]

[0234] In the above formula, R 10 represents an organic residue having an ethylenically unsaturated double bond group having 12 to 20 carbon atoms.

[0235] R 11 represents an oxyalkylene group having 2 to 10 carbon atoms, and preferably represents an oxyethylene group.

[0236] When the reactive emulsifier is a reactive emulsifier represented by the above formula, the product stability of the aqueous dispersion (repellent composition) is improved without decreasing the water repellency. As the reactive emulsifier represented by the above formula, preferably, polyoxyethylene alkylphenol and the like are used.

[0237] The emulsifiers can be used alone or in combination of two or more kinds.

[0238] The mixing ratio of the emulsifier may be, for example, 5 parts by weight or more and, for example, 18 parts by weight or less, relative to 100 parts by weight of the total amount of the monomers.

[0239] The mixing ratio of the emulsifier may be, for example, 8 parts by weight or more and, for example, 20 parts by weight or less, relative to 100 parts by weight in total of the isocyanate derivative (B) and the non-fluorinated copolymer (A).

[0240] The blending ratio of the emulsifier may be, for example, 0.5% by weight or more and, for example, 5% by weight or less, relative to the water repellent composition.

[0241] After the above-mentioned components are mixed, the mixture is stirred and ultrasonic waves are applied to the mixture to emulsify it.

[0242] 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.

[0243] The 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, 0.5 minutes or more and, for example, 10 minutes or less, preferably 5 minutes or less. The stirring temperature is, for example, 50°C or more and, for example, 90°C or less.

[0244] Next, in the case where a portion of the monomers was blended when the above-mentioned mixed liquid was prepared, the remainder of the above-mentioned monomers is blended into this mixed liquid.

[0245] Next, a polymerization initiator is added to this mixture.

[0246] Examples of the polymerization initiator include azo compounds such as azobisisobutylamidine dihydrochloride and azobisisobutyronitrile; water-soluble polymerization initiators such as persulfates such as potassium persulfate and ammonium persulfate; and oil-soluble polymerization initiators such as organic peroxides such as benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate. Preferably, the azo compounds are used. More preferably, the azobisisobutyronitrile is used.

[0247] The mixing ratio of the polymerization initiator may be, for example, 0.01 parts by weight or more, and for example, 10 parts by weight or less, relative to 100 parts by weight of the monomer.

[0248] If necessary, a chain transfer agent can be added to this mixture.

[0249] Examples of the chain transfer agent 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.

[0250] The mixing ratio of the chain transfer agent may be, for example, 0.01 parts by weight or more and, for example, 10 parts by weight or less, relative to 100 parts by weight of the monomer.

[0251] Then, this mixture is heated to polymerize the monomers.

[0252] The heating conditions are such that the heating temperature is, for example, 40° C. or higher and, for example, 80° C. or lower, and the heating time is, for example, 1 hour or higher and, for example, 6 hours or lower. As a result, an emulsion of the non-fluorinated copolymer (A) is obtained, and a water repellent composition containing the isocyanate derivative (B) and the non-fluorinated copolymer (A) (emulsion) is obtained.

[0253] In the first method, the monomers constituting the non-fluorinated copolymer (A) are polymerized in the presence of the isocyanate derivative (B), but the isocyanate derivative (B) can also be blended after the monomers have been polymerized (second method). Also, the isocyanate derivative (B) can be blended after the monomers have been polymerized in the presence of a surfactant and a liquid medium (third method).

[0254] The third method is the same as the above-mentioned production method, except that the monomers constituting the above-mentioned non-fluorinated copolymer (A) are polymerized in the absence of the isocyanate derivative (B). The non-fluorinated copolymer (A) obtained by the third method can be combined with the isocyanate derivative (B) to obtain the water-repellent composition of the present disclosure.

[0255] Alternatively, a monomer may be polymerized to prepare a non-fluorinated copolymer (A), and then the obtained non-fluorinated copolymer (A) may be blended with an isocyanate derivative (B) (fourth method). Alternatively, a monomer may be polymerized to prepare a non-fluorinated copolymer (A), and then the obtained non-fluorinated copolymer (A) may be blended with an isocyanate derivative (B), a surfactant and a liquid medium (fifth method).

[0256] In the fourth and fifth methods, examples of the polymerization method include solution polymerization, suspension polymerization, and emulsion polymerization.

[0257] When solution polymerization is employed, the monomers are dissolved in an organic solvent in the presence of the above-mentioned polymerization initiator, and the resulting solution is heated with stirring after replacing the atmosphere with nitrogen.

[0258] The polymerization initiator may be any of the above-mentioned polymerization initiators. The mixing ratio of the polymerization initiator may be, for example, 0.01 parts by weight or more and, for example, 20 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the monomer.

[0259] Examples of the organic solvent include the solvents listed in the liquid medium described above. The organic solvent may be, for example, glycol (e.g., glycol having 2 to 40 carbon atoms, specifically, ethylene glycol, propylene glycol, etc.), ester (e.g., ester having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketone (e.g., ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), alcohol (e.g., alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, isopropyl alcohol). As the organic solvent, a water-soluble glycol-based solvent (e.g., ethylene glycol, propylene glycol, etc.) may be preferably used.

[0260] The mixing ratio of the organic solvent may be, for example, 10 parts by weight or more, preferably 50 parts by weight or more, and for example, 2000 parts by weight or less, preferably 1000 parts by weight or less, relative to 100 parts by weight of the monomer.

[0261] Regarding the heating conditions, the heating temperature may be, for example, 30° C. or higher and, for example, 120° C. or lower, and the heating time may be, for example, 1 hour or higher and, for example, 10 hours or lower.

[0262] In this manner, the fluorine-free copolymer (A) is obtained.

[0263] After producing the non-fluorinated copolymer (A) by solution polymerization, the organic solvent is removed, and the non-fluorinated copolymer (A) is blended together with the isocyanate derivative (B) with a surfactant and a liquid medium to prepare an emulsion of the non-fluorinated copolymer (A).

[0264] <Uses of the water repellent composition> Examples of applications of the water repellent composition in 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, particularly a water repellent), an antifouling agent, a soil release agent, a stripping agent, a release agent (an external release agent or an internal release agent), and the like.

[0265] <Manufacturing method of treated products> A method of making a treatment product according to the present disclosure includes applying a water repellent composition according to the present disclosure to a substrate, particularly a fibrous substrate.

[0266] [Processing products] Examples of substrates treated with the water repellent composition of the present disclosure include textile products, stone materials, 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, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plasters. Examples of textile products include various types of natural fibers from animals and plants, such as cotton, hemp, 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 fibers, carbon fibers, and asbestos fibers, or mixed fibers thereof. As an example of a substrate to be treated with the water repellent composition, an example of a woven or knitted fabric will be described in detail.

[0267] (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 green fabric, and then post-processing and water-repellent processing the same. The weaving or knitting can be performed using a known weaving machine or knitting machine, and the preparation process prior to the weaving or knitting can also be performed using known equipment.

[0268] In the 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 by a continuous or batch method. Usually, it is preferable to carry out the scour and relaxation by a batch method at 100°C or less, and it is particularly preferable to carry out the scour and relaxation using a high-pressure liquid jet dyeing machine equipped with a jet nozzle.

[0269] After scouring and relaxing, the woven or knitted fabric is preset. Presetting is usually done by dry heat treatment at 170-200℃ for 30-120 seconds using a pin tenter. After presetting, the fabric is dyed according to the usual method, and then a final setting is performed if necessary.

[0270] 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 based on a padding method, a spray method, a kiss roll coater method, a slit coater method, or the like, and then a dry heat treatment is performed at 105 to 190°C for 30 to 150 seconds. The aqueous solution may also contain a crosslinking agent, a softener, an antistatic agent, or the like as necessary. After the water-repellent treatment, the woven or knitted fabric may be calendered to further improve the water-repellent performance.

[0271] The woven and knitted fabrics are suitably used for clothing applications, particularly for uniform wear, ladies' wear, and sportswear.

[0272] 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 arranged so that the woven or knitted fabric side is exposed to rainwater or the like.

[0273] Breathable waterproof layer The moisture-permeable waterproof layer is a layer that covers one side of the woven or knitted fabric and is made of a resin that has waterproof and moisture-permeable properties.

[0274] The moisture-permeable waterproof layer may be formed by applying a resin (resin constituting 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 described later. In the present disclosure, a mixed fiber intertwined yarn having fine 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, and an anchor effect is exerted, making it even more difficult for the woven or knitted fabric and the moisture-permeable waterproof layer to peel off. When 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 anchor effect may not be exerted sufficiently, and in such a case, the woven or knitted fabric and the moisture-permeable waterproof layer tend to peel off easily.

[0275] The resin constituting the moisture-permeable waterproof layer is not particularly limited, but is preferably composed of polyurethane resin as the main component, and for example, it is preferable that the polyurethane resin is contained in a proportion of 80% by weight or more. Polyurethane resin is generally suitable for forming a resin layer having moisture permeability and waterproofness. Among them, a microporous type is preferable in consideration of moisture permeability, but in cases where it is expected that the layer will be exposed to rain for a long period of time or will be used repeatedly by washing, etc., a non-porous type moisture-permeable urethane may be used instead of a microporous type.

[0276] As the polyurethane resin, a conventionally known resin obtained by reacting a polyisocyanate component with a polyol component can be used.

[0277] 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 moisture-permeable waterproof layer may contain inorganic fine powder in order to ensure the desired moisture permeability.

[0278] 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 the inorganic fine powder is preferably 3 to 50% by weight, more preferably 5 to 50% by weight, based on the total weight of the moisture-permeable waterproof layer.

[0279] The moisture-permeable waterproof layer has a thickness of preferably 5 μm or more, more preferably 10 to 30 μm. When the thickness is within the above range, the waterproof property and moisture permeability are well balanced, and further, there are advantages in terms of texture and tear strength.

[0280] ·Adhesive layer The laminated fabric preferably includes an adhesive layer. In other words, 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 fine protrusions on the surface due to loops or slack. Therefore, the protrusions are firmly entangled with the adhesive layer, and an anchor effect is exerted, making it even more difficult for the woven / knitted fabric and the moisture-permeable waterproof layer to peel off from each other.

[0281] In addition, 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 pinholes and poor 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. In order to prevent this, for example, if the surface of the woven or knitted fabric is smoothed by calendaring, the protrusions or air retaining layer may be reduced, resulting in a decrease in water repellency. Therefore, in the present disclosure, it is preferable that the woven or knitted fabric and the moisture-permeable waterproof layer are laminated via an adhesive layer.

[0282] The type of adhesive constituting the adhesive layer is not particularly limited, but it is preferable that it has excellent compatibility with the moisture-permeable waterproof layer. For example, when a resin mainly composed of polyurethane resin is selected as the resin constituting the moisture-permeable waterproof layer, it is preferable to adopt an adhesive layer made of a polyurethane-based adhesive. The polyurethane-based adhesive may be of any structure such as ether-based, ester-based, or polycarbonate-based, but from the viewpoint of imparting excellent moisture permeability, an ether-based adhesive is preferable.

[0283] 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 shape of the pattern is not particularly limited, but examples include dots, lines, a lattice, a checkered pattern, a tortoiseshell pattern, etc., and it is preferable that any of these patterns are uniformly arranged over the entire surface.

[0284] 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 area occupied by the adhesive is increased, and if it exceeds 100 μm, the manufacturing cost increases and further adhesiveness cannot be expected, so neither is preferable.

[0285] · Lining fabric In the laminated fabric of the present disclosure, a fiber fabric for lining may be laminated on the moisture-permeable waterproof layer (the surface of the moisture-permeable waterproof layer opposite to the surface on which the woven / knitted fabric of the present disclosure is laminated). The fiber fabric for lining can protect the moisture-permeable waterproof layer, and can provide even better waterproofness (water pressure resistance) and strength. In addition, laminating the fiber fabric for lining can suppress the elongation of the laminated fabric as a whole, and therefore it is possible to suppress the reduction of the protruding parts of the mixed fiber composite yarn as a result of the protruding parts being pulled by the elongation of the woven / knitted fabric due to the finishing process after lamination or tension during wearing, etc., and the above-mentioned water repellency can be maintained at a higher level. Furthermore, laminating the fiber fabric for lining can further improve the water repellency.

[0286] Examples of fiber fabrics for lining include various woven fabrics and knitted fabrics. Among them, knitted fabrics are preferred because, compared with woven fabrics, the constituent yarns are more likely to protrude from the surface and the surface is not flat, and the anchor effect is more pronounced, making it less likely to peel off from the moisture-permeable waterproof layer. In particular, tricot knitted fabrics are preferred because they have less stretchability than knitted fabrics with other structures, so the stitch gaps do not become too large and water repellency can be more effectively expressed. In addition, tricot knitted fabrics are also preferred because they can obtain a long grey fabric during knitting, have few seams, and can be evenly layered on the moisture-permeable waterproof layer.

[0287] The material of the fiber constituting the lining fiber fabric is not particularly limited and can be selected as appropriate, but nylon fiber is preferable. This is because acid dyes are generally used in nylon fibers, and migration and sublimation of disperse dyes to the moisture-permeable waterproof layer, which is a problem in polyester fibers and the like that use disperse dyes, is unlikely to occur. The form (long fiber, short fiber, or spun yarn) or fineness of the fiber constituting the lining fiber fabric is not particularly limited and can be selected as appropriate within a range that does not impair the effects of the present disclosure.

[0288] Laminated fabric properties The laminated fabric has excellent waterproofness. A suitable example of the waterproofness of the laminated fabric of the present disclosure is, for example, a water level measured according to the water resistance test specified in JIS L 1092:2009 A method (low water pressure method) of 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, and may be, for example, 50,000 mm or 25,000 mm.

[0289] The laminated fabric has excellent moisture permeability. A suitable example of the moisture permeability of the laminated fabric of the present disclosure is a moisture permeability of, for example, 10,000 g / m2 as measured according to JIS L 1099:2012 B-1 method (potassium acetate method). 2 24h or more, preferably 15000g / m 2 24h or more, more preferably 20,000g / m 2 The upper limit of the moisture permeability is not particularly limited, but is, for example, 40,000 g / m 2 24h or 35,000g / m 2 ·24h·mm are examples.

[0290] In the laminated fabric, interlayer peeling between the woven or 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 or 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. In order to set the peel strength within the above range, for example, a woven or knitted fabric that has not been subjected to calendaring may be used, or an adhesive layer may be provided.

[0291] ·Laminated fabric manufacturing method The method for producing the laminated fabric is not particularly limited, and 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: The second manufacturing method includes a step of forming an adhesive layer on the woven or knitted fabric or the moisture-permeable waterproof layer, and a step of bonding the woven or knitted fabric and the moisture-permeable waterproof layer via the adhesive layer.

[0292] It is preferable that the woven or knitted fabric used in the laminated fabric (i.e., the woven or knitted fabric of the present disclosure described above) maintains the protrusions on the fabric surface as much as possible. For example, when the woven or knitted fabric is subjected to a calendar process to facilitate coating processing or the like, the fine protrusions of the mixed fiber intertwined yarn are crushed to form a flat surface, and a specific water drop rolling angle may not be achieved. Furthermore, when the calendar process is performed, the above air retention layer may not be sufficiently maintained, and the desired water repellency may not be achieved. Therefore, it is preferable to thoroughly consider the conditions of the calendar process. For example, when the woven or knitted fabric is subjected to a calendar process, normal conditions (for example, a temperature of 130° C. or higher and a linear pressure of 200 to 20,000 N / cm) that do not reduce the protrusions of the mixed fiber intertwined yarn too much may be adopted. The calendar process may be performed without heating.

[0293] In the first manufacturing method, the resin constituting the moisture-permeable waterproof layer can be applied to the surface of the woven or knitted fabric by, for example, a coating method. In the coating method, a knife coater or a comma coater can be used. From the viewpoint of providing excellent moisture permeability, it is preferable to obtain the moisture-permeable waterproof layer by a wet method.

[0294] In the second manufacturing method, the adhesive layer can be formed on the woven or knitted fabric or the moisture-permeable waterproof layer by, for example, lamination. In the lamination method, the adhesive layer can be formed by a method using a resin solution or a hot melt method. 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, and then heat-treated to completely react to obtain a film. The release material can be appropriately removed after lamination or aging.

[0295] Then, an adhesive layer is formed on the woven or knitted fabric or the moisture-permeable waterproof layer. For example, in the case of a method using a resin solution, a two-component curing polyurethane resin solution adjusted to a viscosity in the range of 500 to 5000 mPa·s may be applied over the entire surface or in a pattern. The adhesive layer is then dried to form an adhesive layer, and the woven or knitted fabric and the moisture-permeable waterproof layer are bonded together via the adhesive layer, and the two are pressure-bonded or thermo-press-bonded to each other, thereby completing the second manufacturing method.

[0296] 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 it is more preferable for practical use to use one that melts at 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 the viscosity when melted. Then, the molten resin is applied onto the woven or knitted fabric or the moisture-permeable waterproof layer, and is matured while cooling at room temperature to form an adhesive layer. Then, the woven or knitted fabric and the moisture-permeable waterproof layer are bonded together via the adhesive layer and pressed together to carry out the second manufacturing method.

[0297] In the manufacturing method, it is preferable to adopt the second manufacturing method. When the 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, and the water pressure resistance will tend to decrease. In addition, when the woven or knitted fabric is subjected to a calendaring 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, and since a separate examination of the calendaring conditions is required, the process itself may become complicated.

[0298] Thereafter, a fiber fabric for the lining can be laminated onto the moisture-permeable waterproof layer using any suitable known method.

[0299] ·Applications of laminated fabric The laminated fabric has excellent water repellency and moisture-permeable waterproof properties, and the moisture-permeable waterproof layer does not peel off even in harsh environments, so it is suitable for use in fields such as uniform clothing, sports clothing, and outdoor products used outdoors.

[0300] [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 a conventionally known method. The water repellent composition of the present disclosure may be dispersed and diluted in an organic solvent or water as necessary, and attached to the surface of a substrate by a known method such as dip coating, spray coating, foam coating, etc., and then dried. After drying, a textile product to which the solid components of the water repellent composition are attached is obtained. If necessary, it may be applied together with a suitable crosslinking agent and cured. Furthermore, it is also possible to use the water repellent composition of the present disclosure in combination with various additives such as water and / or oil repellents, antislip agents, antistatic agents, texture adjusters, softeners, antibacterial agents, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming assistants, compatibilizers, antifreeze agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, and defoamers. Examples of various additives may be the same as those described in the "other components" of the water repellent composition described above. The concentration of the non-fluorinated copolymer (A) in the treating agent to be contacted with the substrate may be appropriately changed depending on the application, but may be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

[0301] [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.

[0302] Examples of textile products include natural fibers of animal and vegetable origin such as cotton, hemp, wool, silk, etc., synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc., semi-synthetic fibers such as rayon, acetate, etc., inorganic fibers such as glass fiber, carbon fiber, asbestos fiber, etc., or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics, nonwoven fabrics, clothing-type cloth, and carpets, but the treatment may also be performed on fibers, yarns, and intermediate textile products (e.g., slivers or rovings) in a state prior to being made into cloth.

[0303] Examples of paper products include paper made of 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, waste paper pulp such as recycled newsprint, 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 cores, neutral pure 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.

[0304] The water repellent composition can be applied to the textile by any of the methods known for treating textiles (e.g., fabrics) with liquids. 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, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0305] Alternatively, the water repellent composition may be applied to the textile by a cleaning method, such as by laundering or by a dry cleaning method.

[0306] The textile products to be treated may be fabrics, including woven, knitted and nonwoven fabrics, apparel fabrics and carpets, 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 rendering textile products (e.g., synthetic fibers) water repellent.

[0307] 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 kinds.

[0308] Examples of natural fibers include cotton, flax, cellulosic fibers such as pulp, chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as ground wood pulp (GP), pressure-risen ground wood pulp (PGW), and thermomechanical pulp (TMP), chemical pulps such as high yield unbleached softwood kraft pulp (HNKP; N material), bleached softwood kraft pulp (NBKP; N material, NB material), unbleached hardwood kraft pulp (LUKP; L material), and bleached hardwood kraft pulp (LBKP, L material), waste paper pulps such as deinking pulp (DIP) and waste pulp (WP), and semi-chemical pulps (CP).

[0309] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymer polyesters; 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 are acetate and triacetate. Examples of regenerated fibers are rayon, cupro, polynosic rayon, lyocell, and tencel. Examples of inorganic fibers are glass fiber and carbon fiber.

[0310] Alternatively, the textile product may be leather. The manufactured polymer may be applied to the leather from an aqueous solution or emulsion at various stages of the leather processing, for example during the wet processing of the leather or during the 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.

[0311] "Treatment" means that the water repellent composition is applied to a substrate by immersion, spraying, coating, etc. Through the treatment, the non-fluorinated copolymer (A) and the isocyanate derivative (B), which are the active ingredients of the water repellent composition, penetrate into the substrate and / or adhere to the substrate surface. In other words, through the treatment, a substrate (e.g., a textile product) to which the non-fluorinated copolymer (A) and the isocyanate derivative (B) in the water repellent composition of the present disclosure are adhered is obtained.

[0312] [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 fastness to the textile product after treatment with the water repellent composition.

[0313] Examples of pretreatments of textile products include cationization treatment by reaction with a reactive quaternary ammonium salt, anionization treatment such as sulfonation, carboxylation, and phosphation, and acetylation treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment after anionization treatment.

[0314] The method for pretreating a textile product is not limited, and the textile product can be pretreated by a conventionally known method. 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 a known method such as dip coating, spray coating, foam coating, etc., and then dried. 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 a textile product, a method for pretreating a textile product with a hydrocarbon-based water repellent will be described in detail.

[0315] 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, X1 and X 2 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) (hereinafter, also referred to as a "specific functional group").

[0316] M 1 Examples of M include H, K, Na, and ammonium ion which may have a substituent. 2 Examples of X include H, K, Na, and 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.

[0317] 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 constituting the fiber.

[0318] In the case of (i), for example, a functional group-containing fiber 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 specific functional group.

[0319] The material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, hemp, silk, wool, etc., semi-synthetic fibers such as rayon, acetate, etc., synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, polypropylene, etc., and composite fibers, blended fibers, etc. 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.

[0320] In this embodiment, from the viewpoint of improving the water repellency of the obtained textile product, it is preferable to use textile materials containing polyamide and polyester as raw materials, and in particular, it is 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.

[0321] Above -SO3M 1 As the compound having the formula (I), a phenol-based polymer can be used. As such a phenol-based polymer, for example, one containing at least one compound represented by the following general formula can be mentioned.

[0322] [ka] [In formula (2), X 2 Ha-SO3M 3 (In the formula, M 3 represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0323] [ka] [In the formula, M 4 represents a monovalent cation.

[0324] The above M 3 Examples of the cation include H, K, Na, and ammonium ion which may have a substituent.

[0325] The above M 4 Examples of the cation include H, K, Na, and ammonium ion which may have a substituent.

[0326] 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.

[0327] Above - COOM 2 Examples of compounds having the formula include polycarboxylic acid polymers.

[0328] 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.

[0329] Examples of the method for producing a polycarboxylic acid polymer include a method in which a radical polymerization initiator is added to an aqueous solution of the above-mentioned monomer and / or its salt, and the mixture is heated and reacted at 30 to 150° C. for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, 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 the radical polymerization initiator 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 of two or more. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added for the purpose of adjusting the degree of polymerization.

[0330] In addition to the above monomers, copolymerizable monomers can be used in the radical polymerization. Examples of the copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. The acrylates and methacrylates are preferably those having 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 of two or more.

[0331] 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.

[0332] The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, and more preferably from 3,000 to 15,000, from the viewpoint of improving the water repellency of the resulting textile product.

[0333] As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (product name, manufactured by Nicca Chemical Co., Ltd.) and "Ceropol PC-300" (product name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0334] Above -OP(O)(OX 1 )(OX 2 ) is exemplified by a phosphate ester compound 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.

[0335] 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.

[0336] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0337] As the phosphate ester compound, for example, a commercially available product such as "Phosphanol ML-200" (product name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0338] The pretreatment liquid containing one or more compounds having the specific functional group may be, for example, an aqueous solution of the above-mentioned compounds. The pretreatment liquid may also contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0339] Examples of the method for treating the textile material with the pretreatment liquid include padding, immersion, spraying, and coating. Examples of padding include a method using a padding device 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 a method using a coating machine described on pages 473-477 of Dyeing and Finishing Equipment Directory (published by Sen-sha, 1981). Examples of immersion include a method using a batch-type dyeing machine described on pages 196-247 of Dyeing and Finishing Equipment Directory (published by Sen-sha, 1981), and a liquid flow dyeing machine, air flow dyeing machine, drum dyeing machine, winch dyeing machine, washer dyeing machine, cheese dyeing machine, etc. can be used. Examples of the spray treatment include an air spray in which the treatment liquid is sprayed in the form of a mist using compressed air, and a method using an air spray of a liquid pressure atomization type. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be appropriately adjusted in consideration of various conditions such as the purpose and performance. In addition, when the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after it is applied to the fiber material in order to remove the water. There is no particular limit to the drying method, and either a dry heat method or a wet heat method may be used. There is also no particular limit to the drying temperature, and for example, drying may be performed at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes after drying.

[0340] 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 specific functional group (e.g., a phenolic polymer compound, etc.) adsorbed during the process may fall off, so it is preferable to carry out the treatment after reduction soaping after dyeing.

[0341] The treatment temperature in the immersion treatment can be 60 to 130° C. The treatment time can be 5 to 60 minutes.

[0342] 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 weight per 100 parts by weight of the textile material. Within this range, durable water repellency and texture can be simultaneously achieved at high levels.

[0343] The pretreatment liquid is preferably adjusted to a pH of 3 to 5. The pH can be adjusted using a pH adjuster such as acetic acid or malic acid.

[0344] In the pretreatment solution, a salt may be used in combination in order to effectively adsorb the compound having the specific functional group to the fiber material by the salting-out effect. Examples of the salt that can be used include sodium chloride. Examples of suitable salts include sodium carbonate, ammonium sulfate, and sodium sulfate.

[0345] In the functional group introduction step using the 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 removing the compound sufficiently, 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. In addition, it is preferable to thoroughly dry the resulting functional group-containing fiber before contacting it with a hydrocarbon-based water repellent.

[0346] (ii) An example of a fiber in which the specific functional group is directly introduced into the material constituting the fiber is cationic dyeable polyester (CD-PET).

[0347] 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, by a zeta potential / particle size measuring system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0348] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0349] Examples of the present disclosure will be specifically described below, but the present disclosure is not limited to these examples.

[0350] [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.

[0351] 100 No wetting or water droplets were observed on the surface. 90 The surface did not wet, but small water droplets were observed adhering to it. Wetting of small individual water droplets was observed on 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 over the entire front and back surfaces.

[0352] [Slip resistance] The test fabric was tested for warp slippage 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.

[0353] [Preparation of raw materials] (Production Example of Acrylic Polymer-Containing Aqueous Dispersion) Manufacturing Example 1 A 500 ml plastic container was charged with 30 g of a water-soluble glycol solvent as an organic solvent, 120 g of pure water as a liquid medium, 58.2 g of stearyl acrylate as a long-chain aliphatic hydrocarbon group-containing (meth)acrylate, 2 g of sorbitan fatty acid ester as a surfactant, 0.1 g of acetic acid as an organic acid, 2 g of a cationic emulsifier, and 6 g of polyoxyethylene alkyl ether, 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 mixture was transferred to a 500 ml autoclave, and after nitrogen replacement, 0.2 g of lauryl mercaptan as a chain transfer agent and 1.8 g of vinyl chloride as a copolymerizable monomer were charged. Furthermore, 1 g of an azo group-containing water-soluble initiator was added as a polymerization initiator, and the mixture was heated to 60°C and reacted for 4 hours to obtain an aqueous dispersion of an acrylic polymer (hydrocarbon-based water-repellent resin). This dispersion was further diluted with pure water to prepare an aqueous dispersion of a hydrocarbon-based water-repellent resin with a solid content concentration of 30% (more specifically, an aqueous dispersion containing a hydrocarbon-based water-repellent resin, a surfactant, and a liquid medium).

[0354] Manufacturing Examples 2 to 7 Except for changing the compounding recipe according to Table 1, an aqueous dispersion containing an acrylic polymer, a surfactant, and a liquid medium was prepared in the same manner as in Production Example 1.

[0355] [Table 1]

[0356] (Production Example of Polyurethane-Containing Aqueous Dispersion) Production Example 8 1. Synthesis of aliphatic polyisocyanate derivatives In a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, Mitsui Chemicals, product name: Takenate 700), 0.25 parts by mass of 2,6-di(tert-butyl)-4-methylphenol (also known as dibutylhydroxytoluene, BHT, hindered phenol-based antioxidant), and 0.25 parts by mass of tetraphenyl dipropylene glycol diphosphite (organic phosphorous ester, cocatalyst) were mixed under a nitrogen atmosphere in a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube. Then, 10.7 parts by mass of 1,3-butanediol was added to the mixture, and nitrogen was introduced into the liquid phase for 1 hour. The mixture was then heated to 80°C and reacted for 3 hours, and then cooled to 60°C. Then, 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate was added as an isocyanurate catalyst, and reacted for 1.5 hours. Then, 0.04 parts by mass of o-toluenesulfonamide was added to 100 parts by mass of HDI. Then, this reaction mixture was passed through a thin-film distillation apparatus (temperature 150°C, vacuum degree 93.3 Pa) and distilled until the amount of remaining HDI monomer was 0.5% or less, to obtain an aliphatic polyisocyanate derivative (isocyanurate derivative of hexamethylene diisocyanate). The isocyanate group content of the obtained aliphatic polyisocyanate derivative was 20.9%, and the average number of isocyanate functional groups was 3.0.

[0357] 2. Production of Hydrocarbon-Based Polyurethane In a reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, 100.20 g of the aliphatic polyisocyanate derivative, 67.60 g of Kalcol 8098 (stearyl alcohol, manufactured by Kao Corporation) as a long-chain active hydrogen compound, and 22.30 g of oleic alcohol were mixed and reacted in a nitrogen atmosphere at 110°C for 4 hours until the concentration of isocyanate groups reached 3.67%. Next, the reaction liquid was cooled to 80° C., and 9.90 g of N-methyldiethanolamine was added as a cationic active hydrogen compound, followed by reaction at 80° C. for 1 hour. Next, 50.00 g of methyl ethyl ketone was added as a solvent, and the mixture was reacted at 80° C. until disappearance of the isocyanate groups was confirmed by infrared absorption spectroscopy. Next, 57.69 g of methyl ether ketone was added to the reaction liquid, the temperature was raised to 80°C, and the reaction liquid was mixed until completely dissolved, and then cooled to 75°C. Thereafter, 18.96 g of acetic acid was added as an acid compound to neutralize the mixture. Next, while maintaining the reaction solution at 75°C, 800.0 g of ion-exchanged water heated to 70°C was gradually added thereto to emulsify (internal emulsification). Next, the solvent was removed using an evaporator under reduced pressure with a water bath temperature of 60° C. until the solid content concentration reached 20% by weight or more. Next, the solid content excluding the acid compound (acetic acid) was adjusted to 20% by weight with ion-exchanged water to obtain an aqueous dispersion containing polyurethane.

[0358] Production Example 9 In a 500 mL four-neck flask equipped with a stirring rod, a thermometer, and a reflux tube, 116 g of sorbitan tristearate and 150 g of 4-methyl-2-pentanone (MIBK) were charged. Next, in order to remove excess water vapor from this mixture, the mixture was stirred while maintaining the temperature of the mixture at 70°C, refluxed for 1 hour, and then cooled to 50°C. Then, while maintaining stirring, 30 g of Desmodur N-100 (biuret derivative of hexamethylene diisocyanate, Covestro) was dropped into the mixture using a dropping funnel. After the dropwise addition, one drop of dibutyltin dilaurate was added as a catalyst and reacted at 80°C for 1 hour. Next, 25 g of sorbitan monostearate was added, and further reacted at 80°C for 4 hours. Then, after cooling to 60°C, the reaction liquid was collected and slowly mixed with 60°C water containing an arbitrary amount of cationic emulsifier and polyoxyethylene alkyl ether. The mixture was stirred at 6000 rpm for 1 minute using a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. After that, the solvent (MIBK) was removed by a reduced pressure operation, and pure water was added to adjust the concentration, and an aqueous dispersion containing polyurethane with a solid concentration of 20% was obtained.

[0359] Manufacturing Example 10 150g of methyl ethyl ketone (MEK) and 51g of stearyl alcohol were charged into a 500mL four-neck flask equipped with a stirring rod, a thermometer, and a reflux tube. Next, in order to remove excess water vapor from this mixture, the mixture was stirred while maintaining the temperature of the mixture at 70°C, refluxed for 1 hour, and then cooled to 50°C. Then, 30g of Desmodur N3200A (biuret derivative of hexamethylene diisocyanate, manufactured by Covestro) was added to the mixture, and the mixture was further reacted at 80°C for 4 hours. After cooling to 60° C., the reaction liquid was collected and slowly mixed with water containing an arbitrary amount of polyoxyethylene alkyl ether at 60° C. The mixture was stirred at 6000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. Next, the solvent (MEK) was removed under reduced pressure, and then pure water was added to adjust the concentration, to obtain an aqueous dispersion containing polyurethane with a solid content of 20%.

[0360] (Production Example of Silicone-Containing Aqueous Dispersion) Manufacturing Example 11 A 200 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser was charged with 12 g of methyl hydrogen silicone oil (SiH:SiCH3 molar ratio measured by 1H NMR = 50:50) and 0.02 g of platinum catalyst. Next, 36 g of 1-hexacosene was charged into the dropping funnel, and 1-hexacosene was added dropwise from the dropping funnel while maintaining the temperature at 70°C. After the dropwise addition was completed, the reaction was continued for another 3 hours at 70°C. It was confirmed by infrared spectroscopy (IR) that the SiH peak had disappeared, and 47 g of solid silicone polymer was obtained. Next, 28g of silicone polymer, 5.6g of water-soluble glycol solvent, 60g of pure water, 1.7g of sorbitan fatty acid ester, 0.7g of polyoxyethylene alkyl ether, and 0.6g of cationic emulsifier are charged into a 250ml glass container, heated to 75°C, stirred at 2000rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasonic waves for 10 minutes to obtain an aqueous dispersion of silicone polymer. Then, pure water is added to prepare an aqueous dispersion of silicone polymer with a solid content concentration of 30% by weight.

[0361] (Production Example of Wax-Containing Aqueous Dispersion) Manufacturing Example 12 A pressure reactor was charged with 150 g of paraffin wax (melting point 75°C), 350 g of pure water, 4.5 g of polyoxyethylene alkyl ether, and 3 g of sorbitan fatty acid ester, sealed, and heated to 110-120°C with stirring, and then emulsified under high pressure for 30 minutes to prepare a water dispersion of wax. Pure water was then added to prepare a water dispersion of wax with a solid content of 30% by weight.

[0362] Manufacturing Example 13 A reaction vessel was charged with 150g of oxidized polypropylene wax with a melting point of 150°C, an acid value of 44mgKOH / g, and a density of 0.93, 325g of ion-exchanged water, 25g of a surfactant with an HLB of 15, and 5g of a 48% aqueous potassium hydroxide solution, and then sealed. The temperature was raised to 160°C with stirring, and the mixture was emulsified under high pressure for 1 hour, and then cooled to 90°C to obtain an aqueous dispersion of polypropylene wax. Pure water was then added to prepare an aqueous dispersion of polypropylene wax with a solid content of 30% by weight.

[0363] [Examples 1 to 11, Comparative Examples 1 to 4] The above-mentioned aqueous dispersion and hydrophilic particles (average temporary particle size 25 nm, zeta potential +45 mV, turbidity 2.0 ppm) shown in Table 2 were added and mixed to obtain an aqueous dispersion with a solid content concentration of 30% according to the composition weight ratio shown in Table 2. This aqueous dispersion was diluted with tap water to prepare 1000 g of a test liquid with a solid content concentration of 1.0 wt %. Next, test cloths (polyester fabric, nylon fabric) were impregnated with this test liquid and passed through a mangle, and the test cloths were passed through a pin tenter at 160°C for 1 minute, dried and cured, and the above-mentioned tests were performed.

[0364] [Example 12] The above-mentioned aqueous dispersion was mixed with the antibacterial and antifungal agent shown in Table 2 (75 ppm of benzisothiazolin-3-one, and 75 ppm of a mixture of 5-chloro-2-methyl-2H-isothiazol-3-one and 2-methyl-2H-isothiazol-3-one (weight ratio 3:1)) to obtain an aqueous dispersion with a solid content concentration of 30% according to the composition weight ratio shown in Table 2. This aqueous dispersion was diluted with tap water to prepare 1000 g of a test liquid with a solid content concentration of 1.0 wt.%. Next, test cloth (polyester fabric, nylon fabric) was impregnated with this test liquid, passed through a mangle, and the test cloth was passed through a pin tenter at 160°C for 1 minute, dried, cured, and the above-mentioned test was performed.

[0365] [Table 2]

[0366] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims.

Claims

1. A non-fluorinated copolymer (A) comprising a repeating unit derived from a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms, and a repeating unit derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride, a water repellent composition, wherein in the non-fluorinated copolymer (A), the amount of repeating units derived from the monomer (a2) is 1 to 9 wt % based on the total amount of repeating units derived from the monomer (a1) and the repeating units derived from the monomer (a2).

2. The hydrocarbon group in the hydrophobic monomer (a1) is a linear alkyl group having 10 or more carbon atoms. The water repellent composition according to claim 1 ,

3. The hydrophobic monomer (a1) has the formula: CH ２ =C(-R １２ )-C(=O)-Y １１ -(R １１ ) ｋ [In the formula, R １１ is a hydrocarbon group having 2 to 40 carbon atoms, R １２ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y １１ is a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - and -NR'- (R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms) k is 1 to 3. The water repellent composition according to claim 1, wherein the compound is represented by the formula:

4. The water repellent composition of claim 1 comprising a silicone.

5. The water repellent composition according to claim 4, wherein the amount of the silicone is 0.1 to 20 parts by mass per 100 parts by mass of the non-fluorinated copolymer (A).

6. The water repellent composition according to claim 1, wherein in the non-fluorinated copolymer (A), the amount of the repeating units derived from the monomer (a2) is 3 to 7 wt % based on the total amount of the repeating units derived from the monomer (a1) and the repeating units derived from the monomer (a2).

7. The water repellent composition according to claim 1 , further comprising an isocyanate derivative (B).

8. The water repellent composition according to claim 7 , wherein the isocyanate derivative (B) has an alkyl group having 12 to 30 carbon atoms.

9. The water repellent composition according to claim 7, wherein the isocyanate derivative (B) is a polyurethane.

10. The water repellent composition according to claim 7, wherein the amount of the isocyanate derivative (B) is 0.1 to 20 parts by mass per 100 parts by mass of the non-fluorinated copolymer (A).

11. 8. The water repellent composition according to claim 7, wherein the isocyanate derivative (B) is a compound obtained by reacting at least one active hydrogen compound selected from the group consisting of hydrocarbon alcohols, sugar alcohol modifications, and hydroxy acid modifications with at least one raw material isocyanate selected from the group consisting of acyclic aliphatic polyisocyanates and derivatives thereof.

12. The hydrophobic monomer (a1) has the formula: CH ２ =C(-R １２ )-C(=O)-Y １１ -(R １１ ) ｋ [In the formula, R １１ is a hydrocarbon group having 2 to 40 carbon atoms, R １２ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y １１ is a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - and -NR'- (R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms) k is 1 to 3. A compound represented by the formula: The water repellent composition according to claim 1, wherein in the non-fluorinated copolymer (A), the amount of the repeating units derived from the monomer (a2) is 3 to 7 wt % based on the total amount of the repeating units derived from the monomer (a1) and the repeating units derived from the monomer (a2).

13. The hydrophobic monomer (a1) has the formula: CH ２ =CH-C(=O)-Y １１ -R １１ [In the formula, R １１ is an alkyl group having 12 to 25 carbon atoms, Y １１ is -O- or -O-(CH ２ ) m -NH-C(=O)-, and m is an integer of 2 or 4. the chloride monomer (a2) is vinyl chloride, The water repellent composition according to claim 1, wherein in the non-fluorinated copolymer (A), the amount of the repeating units derived from the monomer (a2) is 3 to 7 wt % based on the total amount of the repeating units derived from the monomer (a1) and the repeating units derived from the monomer (a2).

14. A method for producing a textile product, comprising applying the water repellent composition according to any one of claims 1 to 13 to a textile substrate.

15. Prior to 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 ) (O.X. ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.

16. A textile product having the non-fluorinated copolymer (A) in the water repellent composition according to any one of claims 1 to 13 adhered thereto.

17. -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 ) (O.X. ２ ) (wherein, X １ and X ２ each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms), to which a compound having one or more functional groups selected from the group consisting of monovalent groups represented by the formula:

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