Water-repellent composition

Abstract

To provide a water-repellent composition that can impart both good water repellency and good slip resistance to textile products. [Solution] A non-fluorinated copolymer (A) comprising repeating units derived from a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms, and repeating units derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride, A water-repellent composition in which, in the non-fluorine copolymer (A), the amount of repeating units derived from the monomer (a2) is 1 to 9% by weight of the sum of the amount of repeating units derived from the monomer (a1) and the amount of repeating units derived from the monomer (a2).

Description

[Technical Field]

[0001] This disclosure relates to a water-repellent composition. [Background technology]

[0002] Development of non-fluorine-based water repellents is underway to impart water repellency to base materials (especially textile products). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2021 / 132172 [Patent Document 2] Japanese Patent Publication No. 2020-189980 [Overview of the project] [Problems that the invention aims to solve]

[0004] When conventional water-repellent agents are used on textile products, there is a risk that the seams may slip, reducing the reliability of the textile product.

[0005] The present disclosure aims to provide a water-repellent composition that can impart both good water repellency and good slip resistance to textile products. [Means for solving the problem]

[0006] This disclosure includes the following aspects: [Section 1] The nonfluorine copolymer (A) comprises repeating units derived from a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms, and repeating units derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride. A water-repellent composition in which, in the non-fluorine copolymer (A), the amount of repeating units derived from the monomer (a2) is 1 to 9% by weight of the sum of the amount of repeating units derived from the monomer (a1) and the amount of 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. The water-repellent composition described in item 1. [Section 3] The hydrophobic monomer (a1) is given by formula: CH2=C(-R 12 )-C(=O)-Y 11 -(R 11 ) k [In the formula, R 11 It 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 It is a 2-4 valent group composed of at least one directly bonded, 2-4 valent hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2- and -NR'- (where R' is a hydrogen atom or a hydrocarbon group having 1-4 carbon atoms), k is between 1 and 3. A water-repellent composition according to item 1 or 2, wherein the compound is represented by [the specified compound]. [Section 4] A water-repellent composition according to any one of items 1 to 3, comprising silicone. [Section 5] The water-repellent composition according to claim 4, wherein the amount of the silicone is 0.1 to 10 parts by mass per 100 parts by mass of the non-fluorine copolymer (A). [Section 6] The water-repellent composition according to any one of claims 1 to 5, wherein in the non-fluorine copolymer (A), the amount of repeating units derived from the monomer (a2) is 3 to 7% by weight of the sum of the amount of repeating units derived from the monomer (a1) and the amount of repeating units derived from the monomer (a2). [Section 7] The water-repellent agent composition according to any one of Items 1 to 6, further comprising an isocyanate derivative (B). [Item 8] The water-repellent agent composition according to Item 7, wherein the isocyanate derivative (B) has an alkyl group having 12 to 30 carbon atoms. [Item 9] The water-repellent agent composition according to Item 7 or 8, wherein the isocyanate derivative (B) is polyurethane. [Item 10] The water-repellent agent composition according to any one of Items 7 to 9, wherein the amount of the isocyanate derivative (B) is 0.1 part by mass to 10 parts by mass per 100 parts by mass of the non-fluorine copolymer (A). [Item 11] The water-repellent agent 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-modified products, and hydroxy acid-modified products with at least one raw material isocyanate selected from the group consisting of acyclic aliphatic polyisocyanates and derivatives thereof. [Item 12] The hydrophobic monomer (a1) has the formula: CH2=C(-R 12 )-C(=O)-Y 11 -(R 11 ) k <映画 [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 divalent to tetravalent group composed of at least one selected from a direct bond, a hydrocarbon group having 1 carbon atom with 2 to 4 valences, -C6H4-, -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.] It is a compound represented by The water-repellent composition according to item 1, wherein in the non-fluorine copolymer (A), the amount of repeating units derived from the monomer (a2) is 3 to 7% by weight of the sum of the amount of repeating units derived from the monomer (a1) and the amount of repeating units derived from the monomer (a2). [Section 13] The hydrophobic monomer (a1) is given by formula: CH2=CH-C(=O)-Y 11 -R 11 [In the formula, R 11 This is an alkyl group having 12 to 25 carbon atoms. Y 11 is -O- or -O-(CH2) m -NH-C(=O)-, m is an integer of 2 or 4. The compound is represented by ] The chloride monomer (a2) is vinyl chloride, The water-repellent composition according to item 1, wherein in the non-fluorine copolymer (A), the amount of repeating units derived from the monomer (a2) is 3 to 7% by weight of the sum of the amount of repeating units derived from the monomer (a1) and the amount of repeating units derived from the monomer (a2). [Section 14] A method for producing a textile product, comprising applying a water-repellent composition described in any one of items 1 to 13 to a textile substrate. [Section 15] Before applying the water-repellent composition to the fiber substrate, the fibers -SO3 M 1 (In the formula, M 1 (represents a monovalent cation) a monovalent group represented by -COOM 2 (In the formula, M 2 (where represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2A method for producing a textile product according to claim 14, comprising the step of imparting one or more functional groups selected from the group consisting of monovalent groups (each representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms). [Section 16] A textile product to which the non-fluorine copolymer (A) in the water-repellent composition described in any one of items 1 to 15 is attached. [Section 17] -SO3 M 1 (In the formula, M 1 (represents a monovalent cation) a monovalent group represented by -COOM 2 (In the formula, M 2 (where represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 The textile product according to item 16, to which a compound having one or more functional groups selected from the group consisting of monovalent groups (each independently representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) is attached. [Effects of the Invention]

[0007] The water-repellent compositions in this disclosure can impart both good water repellency and good slip resistance to substrates (especially textile products). [Modes for carrying out the invention]

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

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

[0010] In this specification, unless otherwise stated, whether or not the phrases "independently in each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition shall apply independently to each occurrence.

[0011] The chemical structures described herein should be understood to exclude any chemical structures that would be considered chemically impossible or extremely unstable by those skilled in the art.

[0012] <Water-repellent composition> The water-repellent composition in this disclosure comprises a non-fluorinated copolymer (A) comprising repeating units derived from a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms, and repeating units 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 repeating units derived from monomer (a2) is 1 to 9% by weight of the sum of the amount of repeating units derived from monomer (a1) and the amount of repeating units derived from monomer (a2). The water-repellent composition in this disclosure can adhere to a substrate (especially textile products) to 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 (silicone, wax, organic acid, surfactant, organic solvent, etc.).

[0014] [(A) Non-fluorine copolymer] The non-fluorinated copolymer (A) does not contain fluorine atoms.

[0015] Non-fluorinated copolymer (A) is Repeating units derived from hydrophobic monomer (a1), and Repeating units derived from chloride monomer (a2) It includes. The non-fluorine copolymer (A) further Cyclic hydrocarbon group-containing monomer (a3), and / or Crosslinkable monomer (a4) It may also contain. The non-fluorine copolymer (A) may also contain other monomers (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, and 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) is given by formula: CH2=C(-R 12 )-C(=O)-Y 11 -(R 11 ) k [In the formula, R 11 It 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 It is a 2-4 valent group composed of at least one directly bonded, 2-4 valent hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2- and -NR'- (where R' is a hydrogen atom or a hydrocarbon group having 1-4 carbon atoms), k is between 1 and 3. It may be a monomer represented by .

[0019] R 11 The hydrocarbon group is preferably a branched or linear (preferably a long-chain linear) hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, and especially an alkyl group. The -CH3 group has a lower surface free energy than -CH2- and tends 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), especially a t-butyl group or isopropyl group, a highly branched group, or a long-chain hydrocarbon group (or a long-chain linear hydrocarbon group), for example, an alkyl group. 11 The number of carbon atoms 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 preferably 10 or more. 11 The number of carbon atoms may be 40 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 12 or less.

[0020] k is 1, 2, or 3. 11 When it has a tetravalent hydrocarbon group with 1 carbon atom, k=3. 11 When it has a trivalent hydrocarbon group with 1 carbon atom, k=2. 11 If it does not have trivalent and tetravalent carbon-1 hydrocarbon groups (for example, Y 11k=1 when it has a divalent 1-carbon hydrocarbon group (-CH2-) (for example, 1 to 6 of them).

[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 include hydrogen atoms, methyl groups, chlorine atoms, bromine atoms, iodine atoms, and cyano groups. 12 R is preferably a hydrogen atom, a methyl group, or a chlorine atom. 12 It is more preferable that it be a methyl group. 12 The presence of a methyl group provides higher liquid repellency. 12 This can be a hydrogen atom, especially from the standpoint of reactivity.

[0022] Y 11 It is preferable that the group is divalent. Examples of divalent to tetravalent hydrocarbon groups with 1 carbon atom include -CH2-, -CH= with a branched structure, and -C≡ with 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, Y' is independently a direct bond, -O-, -NR'- (where 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 from 1 to 5), a linear hydrocarbon group having an unsaturated bond with 1 to 5 carbon atoms, a branched hydrocarbon group having 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l -(l is an independent integer between 0 and 5, and -C6H4- is a phenylene group). It's fine to be that way. Y 11 It is preferable that the group is not solely composed of divalent hydrocarbon groups.

[0024] Y 11 Specific examples of this are -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-(CH)2 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- [where m is an integer from 1 to 5, particularly 2 or 4].

[0025] Y 11 is -O-, -NH-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -O-C(=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 -O-C(=O)-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -NH-C(=O)-NH- [where m is an integer from 1 to 5, particularly 2 or 4.] is preferred. Y 11 is -O-, -O-(CH2) m -O-C(=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-, particularly -O-(CH2) m -NH-C(=O)- is more preferred.

[0026] Y 11 is -O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, or -O-(CH2) m -NH-C(=O)- [where m is an integer from 1 to 5, particularly 2 or 4.] is even more preferred.

[0027] Y 11It is particularly preferable that the compound is -O- or -O-(CH2)2-NH-C(=O)-.

[0028] The hydrophobic monomer (a1) is preferably free of reactive or hydrophilic groups. Examples of reactive groups include epoxy groups, chloromethyl groups, bromomethyl groups, iodomethyl groups, isocyanate groups, and blocked isocyanate groups. Examples of hydrophilic groups include hydroxyl groups, polyalkylene oxide groups, amino groups, carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, alkali metal or alkaline earth metal bases of carboxylic acids, sulfonic acids, phosphoric acid, chlorine or bromine, ammonium bases with iodide ions as counteranions, and other ionic groups. Here, reactive groups and hydrophilic groups may overlap.

[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, and 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, and preferably 3 g / L or less.

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

[0031] Specific examples of hydrophobic monomers (a1) are as follows. The compounds with the following chemical formulas are acrylic compounds in which the α-position is a hydrogen atom, but they may also be methacrylic compounds in which the α-position is a methyl group, or α-chloroacrylic compounds 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 between 3 and 40, and m is a number between 1 and 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, eicosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, eicosyl α-chloroacrylate, behenyl α-chloroacrylate, stearamidoethyl (meth)acrylate, 2-stearamidoethyl acrylate, CH2=CHC(=O)OC2H4NHSO2C 18 H 37 These are some examples. They may be used individually or in combination of two or more.

[0033] From the viewpoint of liquid repellency, the hydrophobic monomer (a1) may include hydrophobic monomers (a1) having an amide group, a urea group, or a urethane group. A combination of hydrophobic monomers (a1) having an amide group, a urea group, or a urethane group and hydrophobic monomers (a1) without an amide group, a urea group, or a urethane group is also possible. An example of a hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group is 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 11CH2=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 Examples include the hydrophobic monomer (a1), CH2=C(-R 12 )-C(=O)-O-(CH2) m -NH-C(=O)-R 11 It may include.

[0034] ((a2) Chloride monomer) The non-fluorinated copolymer (A) contains repeating units 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 non-fluorinated copolymer (A) may have repeating units 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, for example, it may have 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, and is preferably aliphatic. The cyclic hydrocarbon group may be saturated or unsaturated, and is preferably saturated. The cyclic hydrocarbon group may be monocyclic, polycyclic, or crosslinked, and is preferably a crosslinked. The cyclic hydrocarbon group may have a chain-like group (for example, a linear or branched hydrocarbon group).

[0038] The number of carbon atoms in the cyclic hydrocarbon group may be 4 or more, 6 or more, or 8 or more, and may be 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less.

[0039] Specific examples of cyclic hydrocarbon groups include cyclohexyl group, t-butylcyclohexyl group, adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, bornyl group, isobornyl group, norbornyl group, dicyclopentanyl group, dicyclopentenyl group, benzyl group, phenyl group, naphthyl group, 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (e.g., cyclohexylene group, adamantylene group, phenylene group, naphthylene group, etc.), and substituted groups thereof.

[0040] Specific examples of cyclic hydrocarbon group-containing monomers (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 obtained by substituting these acrylates with acrylamide. These may be used alone or in combination of two or more.

[0041] ((a4) Crosslinkable monomers) The non-fluorinated copolymer (A) may have repeating units derived from the 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 a reactive group and an olefinic carbon-carbon double bond. 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, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0043] Examples of reactive groups include hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, carbonyl groups, and isocyanate groups (blocked isocyanate groups).

[0044] Specific examples of crosslinkable monomers (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 obtained by substituting these acrylates with acrylamide. These may be used alone or in combination of two or more. These may be used individually or in combination of two or more.

[0045] ((a5) Other monomers) The non-fluorinated copolymer (A) may contain repeating units derived from monomers (a1) to (a4) other than monomer (a5).

[0046] Other specific examples of monomers (a5) include, for example, ethylene, halogenated olefins, vinyl acetate, acrylonitrile, alkoxypolyalkylene glycol (meth)acrylate, and vinyl alkyl ethers. Other non-fluorinated monomers are not limited to these examples. These may be used alone or in combination of two or more.

[0047] (Composition of polymer) The amount of 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 or more, 80% by weight or more, or 85% by weight or more, relative to the nonfluorine copolymer (A). The amount of 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, relative to the nonfluorine copolymer (A).

[0048] The proportion of hydrophobic monomers (a1) having an amide group, a urea group, or a urethane group among 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 proportion of hydrophobic monomers (a1) having an amide group, a urea group, or a urethane group among 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 repeating units 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, relative to the nonfluorine copolymer (A). The amount of repeating units 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, relative to the nonfluorine copolymer (A).

[0050] In the nonfluorine copolymer (A), the amount of repeating units 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, and preferably 3% by weight or more, relative to the sum of the amount of repeating units derived from the hydrophobic monomer (a1) and the amount of repeating units derived from the chloride monomer (a2).

[0051] In the non-fluorinated copolymer (A), the amount of repeating units derived from the chloride monomer (a2) may be 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, with respect to the sum of the amount of repeating units derived from the hydrophobic monomer (a1) and the amount of repeating units derived from the chloride monomer (a2), preferably 7% by weight or less, and more preferably 5% by weight or less.

[0052] The amount of repeating units 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, relative to the non-fluorinated copolymer (A). The amount of repeating units 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, relative to the non-fluorinated copolymer (A).

[0053] The amount of 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, relative to the nonfluorine copolymer (A). The amount of 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, relative to the nonfluorine copolymer (A).

[0054] The amount of repeating units derived from other monomers (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, relative to the nonfluorine copolymer (A). The amount of repeating units derived from other monomers (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, relative to the nonfluorine copolymer (A).

[0055] The amount of repeating units derived from 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, per 100 parts by weight of repeating units derived from hydrophobic monomer (a1). The amount of repeating units derived from 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, per 100 parts by weight of repeating units derived from hydrophobic monomer (a1).

[0056] The amount of 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, per 100 parts by weight of repeating units derived from the hydrophobic monomer (a1). The amount of 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, per 100 parts by weight of repeating units derived from the hydrophobic monomer (a1).

[0057] The amount of 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, per 100 parts by weight of repeating units derived from the hydrophobic monomer (a1). The amount of 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, per 100 parts by weight of repeating units derived from the hydrophobic monomer (a1).

[0058] The amount of repeating units derived from other monomers (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, per 100 parts by weight of repeating units derived from hydrophobic monomer (a1). The amount of repeating units derived from other monomers (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, per 100 parts by weight of repeating units derived from hydrophobic monomer (a1).

[0059] [(B) Isocyanate derivatives] The isocyanate derivative (B) is a compound obtained by the reaction of an active hydrogen compound with a starting isocyanate, and has a portion derived from the active hydrogen-containing compound and a portion derived from the starting isocyanate. Unlike isocyanate-based curing agents, the isocyanate derivative (B) does not usually have an isocyanate group.

[0060] The isocyanate derivative (B) has an -NHCO- group formed by the reaction of an active hydrogen compound with the starting isocyanate (where -NHCO- may be part of a urethane group or a urea group). The -NHCO- group is formed by the reaction of an active hydrogen-containing group (typically a hydroxyl group) of compound (a) with an active hydrogen-reactive group (typically an isocyanate group) of compound (b). The isocyanate derivative (B) is typically a urethane (especially 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 an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group), is preferred. 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 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 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 linear, and particularly linear. The alkyl group of the isocyanate derivative (B) may have 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more carbon atoms, preferably 12 or more, or 16 or more. The alkyl group of the isocyanate derivative (B) may have 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less carbon atoms, preferably 30 or less, 25 or less, or 20 or less carbon atoms.

[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 1,000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, or 5000 or less.

[0064] The water contact angle of the isocyanate derivative (B) may be 50° or higher, 55° or higher, 65° or higher, 75° or higher, 85° or higher, 90° or higher, 100° or higher, or 105° or higher, 110° or higher, or 115° or higher. The water contact angle of the isocyanate derivative (B) may be 160° or lower, 140° or lower, 130° or lower, 120° or lower, 110° or lower, 100° or lower, or 90° or lower. By having a water contact angle of the isocyanate derivative (B) above the lower limit, good water repellency can be imparted 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.

[0065] [Active hydrogen compounds] Active hydrogen compounds contain active hydrogen groups that react with isocyanate groups.

[0066] Examples of active hydrogen groups include hydroxyl groups, amino groups, and carboxyl groups, but typically it is the hydroxyl group.

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

[0068] The hydrocarbon group in hydrocarbon alcohol (α1) may be a hydrocarbon group having 6 to 40 carbon atoms as described above, and the above explanation shall apply. The hydrocarbon group in hydrocarbon alcohol (α1) may preferably be an alkyl group having 12 to 30 carbon atoms as described above, and the above explanation shall apply.

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

[0070] Examples of hydrocarbon alcohols (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 isomiristyl alcohol, isocetyl alcohol, isostearyl alcohol, and isoicosyl alcohol; linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, icocenyl alcohol, dococenyl alcohol, tetracocenyl alcohol, hexacocenyl alcohol, and octacocenyl alcohol; and branched unsaturated hydrocarbon group-containing active hydrogen compounds such as phytol.

[0071] Here, a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol may be used in combination. When a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol are used in combination, the blending ratio of the 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 also, 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 the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. The blending ratio of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 10 parts by weight or more, preferably 20 parts by weight or more, and also, for example, 60 parts by weight or less, preferably 45 parts by weight or less, and more preferably 30 parts by weight or less, based on 100 parts by weight of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. If the proportion of linear saturated hydrocarbon group-containing alcohol is above the lower limit mentioned above, the crystallinity of the hydrocarbon group will improve, and as a result, the water repellency of the water-repellent treated product treated with this water-repellent composition may be improved.

[0072] [(α2) sugar alcohol / hydroxy acid modified compound] The active hydrogen compound may be a sugar alcohol / hydroxy acid modified product (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, while examples of hydroxy acids include hydroxypolycarboxylic acids. The sugar alcohol / hydroxy acid may be a substance that exists in living organisms. Examples of sugar alcohols / hydroxy acids include compounds derived from aldoses and ketoses, such as tetrose, pentose, hexose, and heptose, but are not limited to these. Specific examples include glucose, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, glycerol, galactose, talose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol, threitol, glucopyranose, and mannopyranose. Examples include sugar alcohols, taropyranose, allopyranose, altropyranose, idopyranose, globyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fusitol, iditol, inositol, pentaerythritol, dipentaerythritol, boremitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, citric acid, gluconate lactone, glyceric acid lactone, xylonate lactone, glucosamine, galactosamine, or mixtures thereof. The number of carbon atoms in 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 greater than 0 to about 230, preferably about 10 to about 175, most preferably about 25 to about 140.

[0073] The sugar alcohol / hydroxy acid modified product (α2) may have 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more hydrocarbon groups having 6 to 40 carbon atoms. The sugar alcohol / hydroxy acid modified product (α2) may have 12 or fewer, 9 or fewer, 6 or fewer, or 3 or fewer hydrocarbon groups having 6 to 40 carbon atoms. The hydrocarbon groups in the sugar alcohol / hydroxy acid modified product (α2) may be the hydrocarbon groups having 6 to 40 carbon atoms as described above, and the above explanation applies. The sugar alcohol / hydroxy acid modified product (α2) may also have an alkyl group having 12 to 30 carbon atoms. The above explanation applies to alkyl groups having 12 to 30 carbon atoms.

[0074] In the sugar alcohol / hydroxy acid modified product (α2), at least one active hydrogen (e.g., hydrogen in the OH group, carboxyl group) of the sugar alcohol and / or hydroxy acid is -R α2 , -C(O)R α2 -(CH2CH2O) n (CH(CH3)CH2O) m R α2 -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 R may be substituted with an active hydrogen substituent selected from a mixture thereof. α2 is a hydrogen atom or a hydrocarbon group having 6 to 40 carbon atoms, where 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, for example, in a 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 this active hydrogen (e.g., an -OH group) may react with the active hydrogen reactant group (especially an isocyanate group) of compound (b) to form -NHCO-. The 6 to 40 carbon atoms in the sugar alcohol / hydroxy acid modified product (α2) are preferably alkyl groups having 12 to 30 carbon atoms as described above, and the above explanation applies.

[0075] ((α21) sorbitan modified compound) The sugar alcohol / hydroxy acid modified product (α2) may be a sorbitan modified product (α21) obtained by modifying sorbitan with a hydrocarbon group having 6 to 40 carbon atoms, and may particularly be an alkylsorbitan, with sorbitan being -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 compounds substituted with a mixture thereof (where R α2 (A hydrocarbon group has 6 to 40 carbon atoms). For example, sorbitan is -C(O)R α2 The compound may be monosubstituted, disubstituted, or trisubstituted. Here, sorbitan may contain amounts of sorbitol, isosorbide, or other intermediates or by-products. The hydrocarbon group in the sorbitan modified product (α21) may be a hydrocarbon group having 6 to 40 carbon atoms as described above, and the above explanation shall apply. The sorbitan modified product (α21) may have an alkyl group having 12 to 30 carbon atoms. The above explanation shall apply to alkyl groups having 12 to 30 carbon atoms. Commercially available sorbitan such as SPAN can be used as the alkylsorbitan.

[0076] In one embodiment, at least one active hydrogen substituent is -C(O)R α2 It is fine if R α2 The C1 is a linear or branched alkyl group having 6 to 40 carbon atoms, more preferably 7 to 21, and most preferably 11 to 21 carbon atoms. Preferred compounds include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and monosubstituted, disubstituted, and trisubstituted sorbitans derived from mixtures thereof. Particularly preferred compounds include monosubstituted, disubstituted, and trisubstituted sorbitan stearates, or sorbitan behenin.

[0077] In one embodiment, R α2 It may contain at least one unsaturated bond. An example of such a compound (at least one active hydrogen substituent is -C(O)R α2 Selected from, R α2 As an example of a compound containing at least one unsaturated bond, sorbitan trioleate (i.e., in the formula, R α2 -C7H 14 CH=CHC8H 17 Examples include, but are not limited to, palmitoleic acid, linoleic acid, arachidonic acid, and erucic acid, which are monosubstituted, disubstituted, and trisubstituted sorbitans.

[0078] In one embodiment, the sorbitan modified product (α21) has at least one active hydrogen substituent, and the active hydrogen substituent is independently -(CH2CH2O) n (CH(CH3)CH2O) m R α2 or -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 (where m is independently between 0 and 20, and n is independently between 0 and 20, and m+n is greater than 0). Such compounds are known as polysorbates and are marketed under the trademark name TWEEN. These sorbitans are R α2 Therefore, monosubstituted, disubstituted, or trisubstituted compounds can be used. Commercially available polysorbates have each R 2 From various polysorbates where H is unsubstituted, each R α2 It is known to contain a wide range of mixtures, from polysorbates in which the linear or branched alkyl group has 6 to 40 carbon atoms (fully substituted), to mixtures of various substitutions thereof. Examples of such sorbitan modified products (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 trioleates (where R α2 C7H 14 CH=CHC8H 17 Examples include (which are commercially available under the name polysorbate 80). The sorbitan modified product (α21) may contain a mixture of compounds having various active hydrogen substituents, and R α2 A compound containing at least one unsaturated bond, and R α2 It may also contain a mixture with a completely saturated compound.

[0079] ((α22) citrate modified compound) The sugar alcohol / hydroxy acid modified product (α2) may be a citrate modified product (α22) obtained by modifying citrate with a hydrocarbon group having 6 to 40 carbon atoms, and may particularly be an alkyl citrate. For example, the citrate modified product (α22) may exist as a monosubstituted, disubstituted, or trisubstituted product having an alkyl group. The hydrocarbon group in the citrate modified product (α22) may be a hydrocarbon group having 6 to 40 carbon atoms as described above, and the above explanation shall apply. The citrate modified product (α22) may have an alkyl group having 12 to 30 carbon atoms. The above explanation shall apply to alkyl groups having 12 to 30 carbon atoms. A mixture of citrates having active hydrogen substituents of various values ​​may be used, and R α2 A compound having a hydrocarbon group having at least one unsaturated bond, and R α2 It may also contain a mixture with a compound that is a completely saturated hydrocarbon. The citrate-modified compound (α22) is -(CH2CH2O) n (CH(CH3)CH2O) m R α2 Alternatively, -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 It may have an active hydrogen substituent selected from (where R α2 (This refers to a hydrocarbon group having 6 to 40 carbon atoms). Examples of citrate-modified (α22) compounds include, but are not limited to, trialkyl citrates.

[0080] ((α23) Pentaerythritol modified compound) The sugar alcohol / hydroxy acid modified product (α21) may be a pentaerythritol modified product (α23) obtained by modifying pentaerythritol with a hydrocarbon group having 6 to 40 carbon atoms, and may be a monosubstituted, disubstituted, or trisubstituted product having a hydrocarbon group (especially an alkyl group) having 6 to 40 carbon atoms, for example, a dipentaerythriol ester. The active hydrogen substituent is -CH2C[CH2OR α2 ]3 may be included (where R α2 ( is a hydrocarbon group with 6 to 40 carbon atoms). Also, pentaerythritol modified compounds (α23) are compounds having a mixture of hydrocarbon group chain lengths, or R α2 A compound containing at least one unsaturated bond, and R α2 It may contain a mixture with a completely saturated compound. The hydrocarbon group in the pentaerythritol modified product (α23) may be a hydrocarbon group having 6 to 40 carbon atoms as described above, and the above explanation shall apply. The pentaerythritol modified product (α23) may have an alkyl group having 12 to 30 carbon atoms. The above explanation shall apply to alkyl groups 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] Furthermore, the cationic active hydrogen compound (α3) preferably has two or more hydroxyl groups per molecule.

[0083] Examples of cationic groups include tertiary amino groups.

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

[0085] Such cationic active hydrogen compounds can impart good dispersibility to liquid media (e.g., water), and can also introduce cationic groups that have affinity for textile products (described later) into the resin, thereby improving wash durability.

[0086] More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as active hydrogen groups and a tertiary amino group as a 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, as well as trialkanolamines such as N-triethanolamine and N-triisopropanolamine, with N-methyldiethanolamine being preferred.

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

[0089] Examples of acid compounds include organic acids and inorganic acids. Examples of organic acids include acetic acid, lactic acid, tartaric acid, and malic acid, with acetic acid and lactic acid being preferred, and acetic acid being more preferred. Examples of inorganic acids include hydrochloric acid, sulfuric acid, and phosphoric acid, with hydrochloric acid being preferred. Examples of acid compounds include organic acids. If the acid compound contains an organic acid, the water repellency of the water-repellent treated product can be improved by the volatilization of the acid by heat treatment. Furthermore, the volatilization of the acid by heat treatment can improve the wash durability of the textile product from the viewpoint that the cationic group can be more easily adsorbed onto the textile product. [(α4) Other active hydrogen-containing compounds] The active hydrogen compound (α) may also contain other active hydrogen compounds (α4).

[0090] ((α41) compound) The active hydrogen compound (α4) is, R α41 -X α41 [In the formula, In the formula, R α41 teeth, C1-C may contain at least one unsaturated group. 30 Linear 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-functionalized C1-C 30 Linear or branched alkyl, Y - R α411 R α412 R α413 N + -R α414 -(Here, Y is a halide ion, for example, Cl - It is. ), HOS(=O)2-R α414 -, or R α411 R α412 C = N - (where R α411 , R α412 , R α413 Each of them is independently -H and C1-C6 alkyl, and R α414 It 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-(CH2CH2O) s (CH(CH3)CH2O) t -H is an isocyanate-reactive functional group (where R ’ is a -H or monovalent organic group, s is an integer between 0 and 50, t is an integer between 0 and 50, and s+t is greater than 0. The compound may be represented by (α41).

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

[0092] In one embodiment, X α41 -OH, -C(O)OH, -SH, -NH(R ’ ) and R α41 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Linear 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-functionalized C1-C 30 Selected from linear or branched alkyl groups.

[0093] X α41 (R) may be an -OH group, and examples of such compounds (α41) include alkyl alcohols such as propanol and butanol, or aliphatic alcohols including stearyl alcohol. α41 It optionally contains at least one unsaturated group, C1-C 30Alkyl diols or polyols (R) such as linear or branched alkyls, ethanediol, propanediol, butanediol, or hexanediol. α41 These are hydroxy-functional C1-C 30 Alkylene glycol ethers such as linear or branched alkyl 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 These are hydroxy-functional linear or branched C1-C chains. 30 Polyether, polyester polyol (R α41 (These are hydroxy-functional linear or branched polyesters), silicone prepolymer polyols (R α41 (These are hydroxy-functional linear or branched organosiloxanes), N,N-dimethylaminoethanol (R α41 This is amine functional C1~C 30 (Straight-chain or branched-chain alkyl), choline chloride or betaine HCl (R α41 Y - R α411 R α412 R α413 N + -R α414 -is), butanone oxime (R α41 R α411 R α412 Examples include, but are not limited to, polyether polyols (where C=N-). Polyether polyols may contain only EO groups, only PO groups, only THF groups, or mixtures thereof. These polyethers may also exist as block copolymers, such as those specified by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). Polyether glycols preferably have an average molecular weight of about 200 or more, most preferably 350 to 2000.

[0094] X α41This may be -C(O)OH, and examples of such compounds (α41) include fatty acids 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 (R α41 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Hydroxy-containing acids (R) such as linear or branched alkyl, 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. α41 These are hydroxy-functional C1-C 30 (Linear or branched alkyl), and mercaptoalkanoic acids such as mercaptopropionic acid (R α41 This is thiol functionality C1~C 30 Examples include, but are not limited to, linear or branched alkyl groups.

[0095] X α41 This may be -SH, and examples of such compounds (α41) include alkylthiols such as lauryl mercaptan or dodecyl mercaptan (R α41 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Examples include, but are not limited to, linear or branched alkyl groups.

[0096] X α41 This may be -NH(R'), and examples of such compounds (α41) include alkylamines such as diisopropylamine, propylamine, hexylamine, or laurylamine (R α41 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Alkanolamines such as linear or branched alkyl groups, ethanolamine, or propanolamine (R α41These are hydroxy-functional C1-C 30 (Linear or branched alkyl), silicone prepolymer polyamine (R α41 (These are amine-functional linear or branched organosiloxanes), alkyldiamines (R α41 This is amine functional C1~C 30 (R) are linear or branched alkyl groups, and aminoalkanesulfonic acids such as 2-aminoethanesulfonic acid. α41 HO-S(O)2R α414 - is one example, but is not limited to these.

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

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

[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, known chain extenders 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, cyclohexanedimethanol; aliphatic or aromatic diamines or polyamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, diethyltoluenenediamine; phenolic hydroxyl group-containing compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol, and o,o'-diallyl-bisphenol A; and alcohol amines such as aminoethyl ethanolamine, aminopropyl ethanolamine, aminohexyl ethanolamine, aminoethyl propanolamine, aminopropyl propanolamine, and aminohexyl propanolamine.

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

[0101] 〔Raw material isocyanate〕 The isocyanate derivative (B) has a portion derived from the raw material isocyanate.

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

[0103] Aromatic polyisocyanates are compounds having aromatic rings and isocyanate groups. The aromatic rings in an aromatic polyisocyanate may be one or more, two or more, or three or more, and may be five or fewer, four or fewer, or three or fewer.

[0104] Acyclic aliphatic polyisocyanates are aliphatic polyisocyanates that do not have a cyclic structure. Acyclic aliphatic polyisocyanates may have aliphatic hydrocarbon groups having 2 to 20 carbon atoms. The aliphatic hydrocarbon groups having 2 to 20 carbon atoms may be divalent aliphatic hydrocarbon groups. The number of carbon atoms in 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, preferably 4 or more, 6 or more, or 8 or more. The number of carbon atoms in 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, 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 terminus of an alkylene group.

[0105] Cyclic alicyclic polyisocyanates are aliphatic polyisocyanates having a cyclic structure. Cyclic alicyclic polyisocyanates have either an aromatic ring or a carbon ring. Cyclic alicyclic polyisocyanates may also have an aliphatic hydrocarbon group having 2 to 20 carbon atoms. The aliphatic hydrocarbon group having 2 to 20 carbon atoms is described in the same way as described for acyclic aliphatic polyisocyanates above.

[0106] Bridged alicyclic polyisocyanates are polycyclic compounds having a crosslinking structure in their ring structure, such as a methylene group. Bridged alicyclic polyisocyanates may also have aliphatic hydrocarbon groups having 2 to 20 carbon atoms. The aliphatic hydrocarbon groups having 2 to 20 carbon atoms are described in the same way as described for acyclic aliphatic polyisocyanates.

[0107] The raw material isocyanate may be a derivative of the raw material isocyanate. Here, examples of derivatives include isocyanurate derivatives, allophanate derivatives, polyol derivatives, biuret derivatives, urea derivatives, oxadiazinetrione derivatives, carbodiimide derivatives, uretodione derivatives, uretonimine derivatives, and the like.

[0108] The raw material 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 embodiment, the raw material isocyanate may be an isocyanurate derivative or a biuret derivative.

[0110] In one embodiment, the raw material isocyanate may be an acyclic aliphatic polyisocyanate.

[0111] Examples of raw material isocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or mixture thereof) (TDI), phenylene diisocyanate (m-,p-phenylene diisocyanate or mixture thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4' or 2,2'-diphenylmethane diisocyanate or mixture thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or Aromatic polyisocyanates selected from 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatephenyl)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 methyl capeate, 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), Methylenebis(Cyclohexyl isocyanate (4,4'-, 2,4'- or 2,2'-methylenebis(Cyclohexyl isocyanate or mixtures thereof) (Hydrogenated MDI), Methylcyclohex Cyclic alicyclic polyisocyanates selected from diisocyanates (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanate-methyl)cyclohexane (1,3- or 1,4-bis(isocyanate-methyl)cyclohexane or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanates, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), and hydrogenated tetramethylxylylene diisocyanate (hydrated TMXDI); Bridged cyclic alicyclic polyisocyanates selected from norbornene diisocyanate, norbornene diisocyanate methyl, bicycloheptane triisocyanate, diisocyanate methyl bicycloheptane, and di(diisocyanate methyl)tricyclodecane; [ka] [ka] Compounds selected from; and the above isocyanates, biuret-modified polyisocyanates, polymers of polyisocyanates (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptomers, etc.), allophanate derivatives (e.g., allophanate derivatives produced by the reaction of the above polyisocyanates with monohydric or dihydric alcohols), polyol derivatives (e.g., polyol derivatives produced by the reaction of the above polyisocyanates with trihydric alcohols (e.g., trimethylolpropane, etc.) (alcohol adducts, preferably trimethylolpropane) Examples include polyisocyanate adducts, biuret derivatives (for example, biuret derivatives produced by the reaction of the above-mentioned polyisocyanate with water or amines), urea derivatives (for example, urea derivatives produced by the reaction of the above-mentioned polyisocyanate with diamines), oxadiazinetrione derivatives (for example, oxadiazinetrione produced by the reaction of the above-mentioned polyisocyanate with carbon dioxide), carbodiimide derivatives (for example, carbodiimide derivatives produced by the decarboxylation condensation reaction of the above-mentioned polyisocyanate), uretodione derivatives, uretonimine derivatives, etc.

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

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

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

[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 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 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 based on 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% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight, relative to the portion derived from the active hydrogen compound. The amount of the portion derived from the sugar alcohol / hydroxy acid modified product 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.

[0118] The amount of the portion derived from the cationic active hydrogen compound (α3) may be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight, relative to 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, relative to 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% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight 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, relative to the isocyanate derivative (B). The amount of the portion derived from the raw material 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, relative to the isocyanate derivative (B).

[0121] [Amount of isocyanate derivative (B)] The amount of 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 nonfluorine copolymer (A). The amount of 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 nonfluorine copolymer (A).

[0122] 〔silicone〕 The water-repellent composition in this disclosure preferably contains silicone in addition to the hydrophobic monomer (a1). By including silicone, it is possible to achieve a good combination of water repellency and slip resistance.

[0123] Silicone is, 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 of these 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 of these 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 greater than or equal to 0, b represents an integer greater than or equal to 1, and (a+b) is between 5 and 200. It may be a polymer shown in [the formula].

[0124] R 51 and R 53 In this, 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 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group; phenyl group, tolyl group, naphthyl group, or groups in which some or all of the hydrogen atoms bonded to these groups are substituted with halogen atoms, amino groups, cyano groups, etc. 51 and R 53 It is preferable that the group is a methyl group or an ethyl group. R 51 and R 53 In this context, the alkoxy group having 1 to 40 carbon atoms may be linear or branched. Examples of alkoxy groups having 1 to 40 carbon atoms include the methoxy group, ethoxy group, propoxy group, and butoxy group.

[0125] Silicones may have at least one long-chain hydrocarbon group. For example, R in formula (S1) 51 At least one of R 53 At least one of the following, or R 51 and R 53 At least one of each of them may be a long-chain hydrocarbon group, 51At least one of the groups (for example, one) may be a long-chain hydrocarbon group. Here, the long-chain hydrocarbon group may be a saturated hydrocarbon group with 6 or more, 10 or more, 15 or more, or 20 or more atoms, preferably 10 or more or 23 or more atoms. Here, the hydrocarbon group may be linear or branched, and is preferably an alkyl group. Specific examples of hydrocarbon groups are hexyl group (6 carbon atoms), octyl group (8 carbon atoms), lauryl group (12 carbon atoms), myristyl group (14 carbon atoms), stearyl group (18 carbon atoms), behenyl group (22 carbon atoms), tricosyl group (23 carbon atoms), lignoceryl group (tetracosyl group, 24 carbon atoms), cellotyl group (hexacosyl group, 26 carbon atoms), montyl group (octacosyl group, 28 carbon atoms), merisyl group (triacontane group, 30 carbon atoms), and dotriacontane group (32 carbon atoms).

[0126] In terms of being easy to manufacture industrially and readily available, the long-chain hydrocarbon group R 51 and R 53 Other than R 51 and R 53 It is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0127] a is a non-negative integer. In terms of ease of industrial manufacture and availability, a may be 40 or less, 30 or less, or 20 or less, and preferably 30 or less.

[0128] The sum of a and b is between 5 and 200. Preferably, the sum of a and b is between 10 and 100, and more preferably between 40 and 60, in terms of ease of industrial manufacture, availability, and handling. a may be between 0 and 150, for example, 1 and 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] If a or b is 2 or more, there are multiple R 51 and R 52 Each of these may be the same or different.

[0130] R51 and R 53 Base (for example, when expressed by the following formula (S2) R 51 and R 52 Base and R 53 It is preferable that 50 mol% or more of the total number of groups are methyl groups.

[0131] The order of existence of the repeating units enclosed by a or b is not limited to the order shown in the chemical formula, but is arbitrary. That is, the silicone may be a random polymer or a block polymer.

[0132] For example, silicone is given by 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 of these 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 of these independently represents a long-chain hydrocarbon group. R 53 Each of these 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 greater than or equal to 0, b represents an integer greater than or equal to 1, and (a+b) is between 5 and 200. It may be a polymer shown in [the formula]. In equation (S2), R 51 and R 53 It 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 as follows: [ka] [In the formula, a represents an integer between 0 and 150, b represents an integer between 1 and 150. (a+b) is between 5 and 200. n is an integer between 1 and 36 (preferably n is a long-chain hydrocarbon group).

[0134] Silicones can be synthesized by conventionally known methods. For example, a silicone can be obtained by hydrosilylation of an α-olefin with a silicone having an SiH group.

[0135] Examples of silicones having SiH groups include methyl hydrogen silicone with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methyl hydrogen siloxane. Among these, methyl hydrogen silicone is preferred because it is easy to manufacture industrially and readily available. Hydrogen silicone (e.g., methyl hydrogen silicone) is a polydiorganosiloxane in which part of the side chain is replaced with hydrogen, and the hydrogen atoms are directly bonded to silicon atoms. When using hydrogen silicone, a catalyst may be used to improve reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine-based catalysts can be used. Organic acid metal salts are preferred as catalysts, and fatty acids are preferred as organic acids. Zinc stearate can be used from the viewpoint of ease of handling. It is preferable to use the catalyst at a concentration of 10 to 40% relative to the methyl hydrogen silicone, as this makes it easier to exhibit its effect. Two or more types of amino-modified, epoxy-modified, carboxy-modified, and methyl hydrogen silicones may be mixed. All of them are silicones having reactive groups and preferably have film-forming properties. Film-forming properties refer to the ability of a silicone to form a solid film, rather than an oily or gel-like film, after being applied to the fiber surface in an emulsion state.

[0136] Alpha-olefins are compounds from which long-chain hydrocarbon groups are derived in silicones. Specific examples of alpha-olefins include 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triaconthene, and 1-dotriaconthene. The hydrosilylation reaction may be carried out by reacting the α-olefin with the SiH group-containing silicone in a stepwise or one-time manner, if necessary, in the presence of a catalyst.

[0137] The amounts of SiH-containing silicone and 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-containing silicone.

[0138] Examples of catalysts used in hydrosilylation reactions include compounds such as platinum and palladium, with platinum compounds being preferred. Examples of platinum compounds include platinum(IV) chloride.

[0139] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted as appropriate. The reaction temperature is, for example, 10 to 200°C, preferably 50 to 150°C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150°C. Hydrosilylation reactions are preferably carried out under an inert gas atmosphere. Examples of inert gases include nitrogen and argon. The reaction will proceed even without a solvent, but a solvent may be used. Examples of solvents include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0140] (Reactive silicone) The silicone may include a reactive silicone. Examples of reactive silicones include polysiloxanes having reactive groups in the side chain, one end, both ends, or both ends. However, from the viewpoint of having excellent slip resistance and water repellency, a polysiloxane having reactive groups in the side chain and / or both ends may also be used. The reactive silicone is not particularly limited as long as it has reactive groups in the molecule, but examples include amino-modified silicones, epoxy-modified silicones, carboxy-modified silicones, and hydrogen-modified silicones. The reactive silicone may be one in which one or more substituents in the above formula (S1) or formula (S2) are substituted with reactive groups.

[0141] Examples of amino-modified silicones include those having a structure in which an amino group is bonded to an organic group directly attached to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Alkylene groups with 2 or more carbon atoms are preferred. Divalent aromatic groups with 6 or more carbon atoms are preferred. The amino group may be a primary, secondary, or tertiary amino group. Examples of organic groups to which an amino group is bonded include: 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 or at the terminal ends of the polysiloxane.

[0142] Examples of epoxy-modified silicones include those having a structure in which an epoxy group is bonded to an organic group directly attached to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Typically, the bond with the organic group is in the form of a glycidyl ether. Examples of such functional groups include 3-glycidoxypropyl and 2-glycidoxyethyl groups. These functional groups may be located on the side chains or at the terminals of the polysiloxane.

[0143] Examples of carboxylated silicones include those having a structure in which a carboxyl group is bonded to an organic group directly connected to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Alkylene groups with two or more carbon atoms are preferred. Divalent aromatic groups with six or more carbon atoms are preferred. Examples of such functional groups include 3-carboxypropyl and 2-carboxyethyl groups. These functional groups may be located on the side chains or at the terminals of the polysiloxane.

[0144] (Silicone resin) Silicone may contain silicone resin. Silicone resin is R3SiO 1 / 2 Units (M units), RSiO 3 / 2 Units (T units) and SiO 4 / 2 A silicone resin consisting of at least one selected from units (Q units), where R is a linear or branched monovalent alkyl group having 1 to 18 carbon atoms, excluding silicone resins consisting only of M units or only of Q units). Silicone resin (B) is R2SiO 2 / 2 It is preferable to omit the units (D units) from the viewpoint of achieving the effects of this invention.

[0145] The silicone resin is preferably in a sol state. Examples of R include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, cetyl group, stearyl group, etc. However, considering the stability when the silicone resin (B) is in a sol state, the availability of raw materials, and cost, R is preferably a methyl group, and in particular, it is preferable that 90% or more of all R are methyl groups. Note that different types of groups may be used in combination for R.

[0146] R2SiO in silicone resin 2 / 2 The inclusion of units (D units) may impair the low slipperiness of the water-repellent composition. Furthermore, a silicone resin consisting solely of Q units may hinder the water-repellent performance of the water-repellent composition.

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

[0148] Furthermore, silicone resin (B) may contain structural units that include hydroxyl groups bonded to silicon atoms. Specifically, (HO)RSiO 2 / 2 Units, (HO)2RSiO 1 / 2 Unit: (HO)SiO 3 / 2 Unit: (HO)2SiO 2 / 2 Unit: (HO)3SiO 1 / 2 The units may be listed, and some of the hydroxyl groups may be alkoxy groups represented by RO groups.

[0149] A sol containing silicone resin can be obtained by a manufacturing method described in Patent No. 3852921, which involves uniformly dispersing and polymerizing organodisiloxane, tetraalkoxysilane and their partially hydrolyzed condensates in water containing a surfactant, or by a manufacturing method which involves hydrolyzing the silane compounds shown below in water.

[0150] This paper details a manufacturing method for hydrolyzing silane compounds in water. Any silane compound can be used as a raw material for this manufacturing method, as long as it contains one, three, or four hydrolyzable groups, and has an alkyl group that satisfies the above conditions, and the hydrolyzable group is either chlor or alkoxy.Specifically, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrichlorosilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyl Lichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrichlorosilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, 2-ethylhexyltrichlorosilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, decyltriethoxysilane, cetyltrichlorosilane, cetyltrimethoxysilane, cetyltriethoxy Silane, stearyltrichlorosilane, stearyltrimethoxysilane, stearyltriethoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, dimethylethylchlorosilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylpropylchlorosilane, dimethylpropylmethoxysilane, dimethylpropylethoxysilane, dimethylisopropylchlorosilane, dimethylisopropylmethoxysilane, dimethylisopropylethoxysilane, dimethylisopropylethoxysilane, dimethylisopropyl methoxysilane, dimethylisopropylethoxysilane, dimethyl Methylhexylchlorsilane, dimethylhexylmethoxysilane, dimethylhexylethoxysilane, dimethyldecylchlorsilane, dimethyldecylmethoxysilane, dimethyldecylethoxysilane, dimethylcetylchlorsilane, dimethylcetylmethoxysilane, dimethylcetylethoxysilane, dimethylstearylchlorsilane, dimethylstearylmethoxysilane, dimethylstearylethoxysilane, and their partial hydrolysates are examples of usable silane compounds, but the usable silane compounds are not limited to these.Due to ease of handling, ease of removing by-products, and availability of raw materials, it is more preferable to use methoxysilane or ethoxysilane. One or more of these silane compounds may be used.

[0151] Common methods that are generally known can be used to hydrolyze silane compounds in water. These include methods such as adding the silane compound dropwise to water while carrying out the hydrolysis reaction, or mixing the water and silane compound together and then carrying out the hydrolysis reaction. A hydrolysis catalyst may be used when carrying out the hydrolysis reaction. Conventional known catalysts can be used as hydrolysis catalysts, and it is preferable to use acidic or alkaline catalysts. In the case of acidic catalysts, solid acids such as hydrogen halides, carboxylic acids, sulfonic acids, acidic or weakly acidic inorganic salts, and ion exchange resins are preferred. In the case of alkaline catalysts, alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate, alkali metal silanolates such as sodium silanolate and potassium silanolate, amines such as triethylamine, diethylamine, and aniline, and aqueous ammonia can be used. It is preferable to adjust the amount of catalyst added so that the pH of the aqueous solution is 2 to 7 and 7 to 12. After the reaction is complete, a neutralizing agent to neutralize the acidic or alkaline catalyst may be added as needed.

[0152] A surfactant may be added to the aqueous solution to disperse the silane compound and the hydrolysis reaction product in water. There are no particular restrictions on the surfactant, but for example, anionic surfactants such as alkyl sulfates, alkylbenzene sulfons, and alkyl phosphates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene oxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene fatty acid esters; cationic surfactants such as quaternary ammonium salts and alkylamine acetates; and amphoteric surfactants such as alkyl betaines and alkylimidazolines can be used, either alone or in combination of two or more. Furthermore, surfactants that exhibit acidity or alkalinity can also be used as hydrolysis catalysts. There are no particular restrictions on the amount of surfactant to be added, but it is preferable to add 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 will not be sufficiently obtained, and if it is more than 50 parts by weight, the water repellency of the water repellent may be impaired.

[0153] A mixture of water and a silane compound may be mixed with a hydrolysis catalyst and surfactant as needed, and the hydrolysis reaction may be carried out at 0-90°C for 10 minutes to 24 hours. Afterward, a neutralization reaction may be carried out as needed to obtain silicone resin. Alcohols and neutralization salts produced as by-products of the hydrolysis reaction can be removed by vacuum distillation or filtration. Various additives can be incorporated into this silicone resin. For example, preservatives and thickeners 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, per 100 parts by weight of non-fluorine 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, per 100 parts by weight of non-fluorine copolymer (A).

[0155] 〔wax〕 The water-repellent composition in this disclosure preferably contains a wax in addition to the hydrophobic monomer (a1). By including a wax, it is possible to achieve a good combination of water repellency and slip resistance. The water-repellent composition in this disclosure may contain both silicone and wax, or it may contain only one of silicone and wax.

[0156] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, animal and plant waxes, and mineral waxes. Paraffin wax is preferred. Specific examples of compounds constituting the wax are 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-tricocene, 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 compounds 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 individually 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, and 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 wax 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 non-fluorine copolymer (A). The amount of 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, per 100 parts by weight of non-fluorine copolymer (A).

[0159] [Inorganic particles] The water-repellent compositions in this disclosure may contain inorganic particles. Including inorganic particles can provide better water repellency and slip resistance. The inorganic particles may be aluminum compounds (e.g., alumina), silicon compounds (e.g., silica), titanium compounds, etc. These may be used alone or in combination of two or more. The inorganic particles may have a hydrophilic surface treatment or a hydrophobic surface treatment.

[0160] The average primary particle diameter of 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 inorganic particles may be 600 nm or less, 400 nm or less, 200 nm or less, 100 nm or less, 40 nm or less, 37.5 nm or less, 35 nm or less, 32.5 nm or less, 30 nm or less, 27.5 nm or less, 25 nm or less, or 22.5 nm or less, preferably 40 nm or less. Being within the above range allows for a good combination of water repellency and slip resistance. The average primary particle diameter can be measured with a microscope (scanning electron microscope or transmission electron microscope). Specifically, an arbitrary position on the fabric is observed from above at an arbitrary magnification using a microscope. Next, if the particle shape is spherical, its diameter is considered as the particle diameter (particle size); if it is non-spherical, the average of the longest and shortest diameters is considered as the particle diameter (particle size). The particle size of all particles present within the field of view is measured, and this process is repeated by moving the field of view and measuring the particle size again. By doing so, the particle size is measured at 10 or more points, and the average value is taken as the average primary particle diameter.

[0161] (Amount of inorganic particles) The amount of 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, per 100 parts by weight of non-fluorine copolymer (A). The amount of 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, per 100 parts by weight of non-fluorine copolymer (A).

[0162] [Liquid media] 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. Preferably, it is a mixture of water and an organic solvent. By including an organic solvent, a good combination of water repellency and slip resistance can be achieved.

[0163] Examples of organic solvents include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes with 5 to 10 carbon atoms, specifically naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain compounds having at least one hydroxyl group (e.g., polyhydric alcohols such as alcohols and glycol-based solvents, or ether forms of polyhydric alcohols (e.g., monoether forms)). These may be used individually or in combination of two or more.

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

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

[0166] The amount of 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, relative to the liquid medium. The amount of 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, relative to the liquid medium.

[0167] The amount of 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, per 100 parts by weight of non-fluorine copolymer (A). The amount of 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, per 100 parts by weight of non-fluorine copolymer (A).

[0168] The amount of 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, per 100 parts by weight of water. The amount of 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, per 100 parts by weight of water.

[0169] [Dispersant] The water-repellent composition may contain a dispersant to enhance the dispersibility of the non-fluorine copolymer (A). The dispersant may be a polymeric dispersant, preferably a hydrophilic polymeric dispersant. Examples of dispersants include polyvinylpyrrolidone, polyvinyl alcohol, polyglycerin, and polyacrylates. These may be used alone or in combination of two or more.

[0170] (Amount of dispersant) The amount of dispersant 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 non-fluorine copolymer (A). The amount of 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, per 100 parts by weight of non-fluorine copolymer (A).

[0171] [Surfactants] The water-repellent composition preferably contains a surfactant. The surfactant in the water-repellent composition may include a nonionic surfactant. The inclusion of a surfactant allows for a good combination of water repellency and slip resistance. Furthermore, the surfactant may include one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. A combination of a nonionic surfactant and a cationic surfactant is preferred.

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

[0173] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0174] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1-6 valent (especially 2-5 valent) alcohols with 1-50 carbon atoms (especially 10-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0175] Examples of ester ethers are compounds formed by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are 1-6 valent (especially 2-5 valent) alcohols with 1-50 carbon atoms (especially 3-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0176] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolaminos. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols 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] Polyhydric alcohols may be divalent to pentavalent alcohols with 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (a secondary amine or preferably a tertiary amine) (for example, having 5 to 50 carbon atoms).

[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 of the oxyalkylene group is preferably 2 to 10. In general, the number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100. Nonionic surfactants are selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and are preferably nonionic surfactants having an oxyalkylene group.

[0179] Nonionic surfactants may be alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycol esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene oxide adducts of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide adduct and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (which may be random copolymers or block copolymers) are preferred. Furthermore, nonionic surfactants are preferable because they do not contain aromatic groups due to environmental concerns (biodegradability, endocrine disruptors, etc.).

[0180] Nonionic surfactants are defined by the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 This 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 of these is independently identical or distinct, an alkylene group having 3 or more carbon atoms (e.g., 3 to 10). R 3 These are 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 greater than or equal to 2. q is a number greater than or equal to 1, or 0. It may be a compound represented by [the formula shown].

[0181] R1 The carbon atoms have 8 to 20 carbon atoms, and are more preferably 10 to 18 carbon atoms. 1 Preferred specific examples include the lauryl group, tridecyl group, and oleyl group. R 2 Examples include the propylene group and the butylene group. In nonionic surfactants, p may be a number greater than or equal to 3 (for example, 5 to 200). q may be a number greater than or equal to 2 (for example, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic surfactant may be a polyoxyethylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, but among these, oxypropylene chains are preferred.

[0182] Specific examples of nonionic surfactants include ethylene oxide, hexylphenol, isooctatylphenol, hexadecanol, oleic acid, and alkanes (C 12 -C 16 ) Thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl(C 12 -C 18 This includes condensation products with amines, etc.

[0183] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example, 30 to 75% by weight, and especially 40 to 70% by weight, relative to the molecular weight of the nonionic surfactant (copolymer). The average molecular weight of nonionic surfactants is generally between 300 and 5,000, for example, between 500 and 3,000. Nonionic surfactants may be a mixture of compounds with an HLB (hydrophilic-hydrophobic balance) of less than 15 (especially 5 or less) and compounds with an HLB of 15 or more. An example of a compound with an HLB of less than 15 is sorbitan fatty acid ester. An example of a compound with an HLB of 15 or more is polyoxyethylene alkyl ether. The weight ratio of the compound with an HLB of less than 15 to the compound with an HLB of 15 or more may be 90:10 to 20:80, for example, 85:15 to 55:45. Nonionic surfactants may be a single type or a mixture of two or more types.

[0184] (cationic surfactant) The cationic surfactant is preferably a compound that does not have an amide group.

[0185] Cationic surfactants may be amine salts, quaternary ammonium salts, or oxyethylene-added ammonium salts. Specific examples of cationic surfactants are not limited to alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt-type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and quaternary ammonium salt-type surfactants such as benzethonium chloride.

[0186] Preferred examples of cationic surfactants are: R 21 -N + (-R 22 )(-R 23 )(-R 24 ) X - [In the formula, R 21 , R 22 , R 23 and R 24 These are hydrocarbon groups with 1 to 40 carbon atoms. X is an anionic group. It is a compound of [the compound]. R 21 , R 22 , R 23and -R 24 Specific examples of X are alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid, acetic acid). The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl group with 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 (for example, C 12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 These are H or C1-C4 alkyl groups, benzyl groups, and polyoxyethylene groups (number of oxyethylene groups e.g., 1 (especially 2, particularly 3) to 50). (CH3 and C2H5 are particularly preferred.) X is a halogen atom (for example), a C1-C4 fatty acid base, p is either 1 or 2, q is either 2 or 3, and p + q = 4. It may be an ammonium salt represented by R. 1 The number of carbon atoms can be 12 to 50, for example, 12 to 30.

[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-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphate mono or diester type surfactants, and sulfosuccinate esters.

[0190] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, these include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amidopropyl dimethylaminoacetic acid betaine.

[0191] The surfactant may consist of one or more nonionic surfactants, cationic surfactants, and amphoteric surfactants.

[0192] (Amount of surfactant) The amount of surfactant 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 non-fluorine copolymer (A). The amount of 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, per 100 parts by weight of non-fluorine copolymer (A). The amount of cationic surfactant may be 5% by weight or more, preferably 10% by weight or more, and more preferably 20% by weight or more, relative to the total amount of surfactant. The weight ratio of nonionic surfactant to cationic surfactant is preferably 95:5 to 20:80, and more preferably 85:15 to 40:60. The amount of cationic surfactant may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight, per 100 parts by weight of water-repellent resin. The total amount of surfactant may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight, per 100 parts by weight of 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). Alternatively, the curing agent may be added to the water-repellent composition after polymerization to obtain a non-fluorine copolymer (A).

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

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

[0196] Examples of aliphatic polyisocyanates include 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, and 2,6-diiso These include 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, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. 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 individually or in combination of two or more.

[0198] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or mixtures thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used individually or in combination of two or more.

[0199] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate or mixtures thereof, 2,4- or 2,6-tolylenediisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used individually or in combination of two or more.

[0200] Examples of polyisocyanate derivatives include various derivatives of the polyisocyanate compounds described above, such as dimers, trimers, biuretes, allophanates, carbodiimides, uretodiones, uretoimines, isocyanurates, and iminooxadiazinediones. These may be used individually or in combination of two or more.

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

[0202] Blocking agents sequester free isocyanate groups. Blocked polyisocyanate compounds can be easily reacted with hydroxyl groups by heating them to, for example, 100°C or higher, such as 130°C or higher, which regenerates the isocyanate groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. Polyisocyanate compounds can be used alone or in combination of two or more.

[0203] Epoxy compounds are compounds that have an epoxy group. Examples of epoxy compounds include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. A chloromethyl group-containing compound is a compound that has a chloromethyl group. Examples of chloromethyl group-containing compounds include chloromethyl polystyrene. Carboxyl group-containing compounds are compounds that have a carboxyl group. Examples of carboxyl group-containing compounds include (poly)acrylic acid and (poly)methacrylic acid.

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

[0205] (Amount of hardener) The amount of curing agent 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 non-fluorine copolymer (A). The amount of 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, per 100 parts by weight of non-fluorine copolymer (A).

[0206] The silicones, waxes, inorganic particles, liquid media, dispersants, surfactants, or curing agents mentioned above may be added after the production of the non-fluorinated copolymer (A), or the non-fluorinated copolymer (A) may be produced by polymerizing the monomers of the non-fluorinated copolymer (A) in the presence of the silicones, waxes, inorganic particles, liquid media, dispersants, surfactants, or curing agents mentioned above.

[0207] [Other ingredients] The water-repellent composition may contain other components besides those listed above. Other components may be added after the non-fluorine copolymer (A) has been manufactured. Examples of other components include water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components include texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle inhibitors, drying speed regulators, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, wrinkle inhibitors, shape retainers, drape retainers, ironing improvers, whitening agents, whitening agents, fabric softening clay, color transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyldisodium (Chinopearl CBS-X, manufactured by Ciba Specialty Chemicals), dye fixatives, fade inhibitors such as 1,4-bis(3-aminopropyl)piperazine, and stain removers. As fiber surface modifiers, enzymes such as cellulase, amylase, protease, lipase, and keratinase; as antifoaming agents, silk protein powder, surface modifiers thereof, and emulsified dispersions can be used to impart the texture and functionality of silk, such as moisture absorption and release properties. Specifically, K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Solubble S (Ichimaru Falcos), nonionic polymer compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units, such as anti-fouling agents like FR627 from Go-o Chemical Industry and SRC-1 from Clariant Japan can be incorporated. These may be used individually or in combination of two or more.

[0208] (Antistatic agent) Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate esters, phosphonates, and phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and its derivatives; and nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives. These may also be ion-conductive polymers obtained by polymerizing or copolymerizing monomers having cationic, anionic, or amphoteric ion-conductive groups. These may be used individually or in combination of two or more.

[0209] (Antibacterial and antifungal agent) An antibacterial and antifungal agent is at least one antibacterial and antifungal agent that inhibits the growth of microorganisms such as fungi, 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 for Antimicrobial Agents 1998 VOL.26 can be used.

[0210] Amine-based compounds such as Bis(3-aminopropyl)dodecylamine (trialkyltriamine), Alcohol-based substances such as ethyl alcohol (ethanol), isopropyl alcohol (isopropanol), propyl alcohol (propyl alcohol, propanol), tris(hydroxymethyl)nitromethane (trisnitro), 1,1,1-Trichloro-2-methyl-2-propanol (chlorobutanol), and 2-Bromo-2-nitropropane-1,3-diol (pronobol, pronosol, pronocot). Aldehydes such as 1,5-Pentanediol (glutaraldehyde), Formaldehyde, and α-Bromocinnamic aldehyde, Isothiazoline derivatives such as 2-n-Octyl-4-isothiazolin-3-one (Skaene M-8), 5-Chloro-2-methyl-4-isothiazolin-3-one / 2-Methyl-4-isothiazolin-3-one (Kayson CG, NS-500W), 1,2-Benzisothiazolone-3 (BIT), and Nn-Butyl-1,2-benzisothiazolone-3 (n-butyl BIT), Isothiocyanates such as allyl isothiocyanate (aryl isothiocyanate, allyl isothiocyanate), Imidazole derivatives such as 2-(4-Thiazolyl)-benzimidazol (thiabendazole, TBZ) and Methyl-2-benzimidazole carbamate (2-benzimidazolylcarbamate methyl, Preventol BCM), Ester compounds such as glycerol laurate (lauricidine, glyceryl monolaurate, monoglyceride), Oxazolidine derivatives such as 4,4-Dimethyl-1,3-oxazolidine (Biopan CS-1135, Oxazine A), Carbanilides such as 3,4,4'-Trichlorocarbanilide (triclocarban) and 4,4'-Dichloro-3-(3-Fluoromethyl)-carbanilide (halocarban) Carbamate-based compounds such as 3-Iodo-2-propynylbutyl carbamate (glycical), Carboxylic acids such as Benzoic acid (benzene carboxylic acid), Flexa-2,4-dienoic acid (sorbic acid, 2-propanylic acid), Octanoic acid (caprylic acid), Propionic acid (propionic acid), Undecylenic acid (10-undecylenic acid, 10-undecenoic acid), Potassium hexa-2,4-dienoic acid (potassium sorbate, potassium 2-propenylacrylate), Potassium propionate (potassium propionate), Calcium propionate (calcium propionate), Sodium benzoate (sodium benzoate), Sodium propionate (sodium propionate), Magnesate(2-),bis(2-carboxybenzene carboperoxato)dihydrogene (monomagnesium phthalate), Zinc undecylenate (zinc undecylenate), etc. Quinoline derivatives such as 8-Hydroxyquinoline and Bis(quinolin-8-olate)copper (copper quinoline, copper oxine, copper 8-quinolinol), Sulfide-based compounds such as Bis(dimethylthiocarbamoyl)disulfide (TMTD, thiuram), Diphenyl ethers such as 2,4,4'-Trichloro-2'-hydroxydiphenyl (triclosan, irgasan DP300), Sulfamide derivatives such as N,N-Dimethyl-N'-(fluorodichloromethylthio)-N"-phenylsulfamide (cyclofluanide, Preventol A4-S) and N-Dichlorofluoromethylthio-N',N'-dimethyl-Np-torylsulfamide (trifluamide, Preventol A5), Proteins such as protamine (fish milt protein, fish milt hydrolysate, nucleoprotein) and hemoglobin (egg white lysozyme), Thiazoles such as 2-(4-Thiocyanomethylthio)benzothiazol (benthiazole), Thiocarbamate compounds such as sodium N-methyldithiocarbamate (sodium N-methyldithiocarbamate, carbam sodium), Hexahydro-1,3,5-tris(hydroxyethyl)-S-triadine (Biopan GK, triazine) Triazine-based drugs such as CAVINON(100,200) and α-[2-(4-Chlorophenyl)ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol (debuconazole), Tropolone derivatives such as 4-Isopropyl-2-hydroxy-cyclohepta-2,4,6-triene-1-one (hinokitiol, β-thujaplicin), Nitrile-based compounds such as 2,4,5,6-Tetrachloroisophthalonitrile and 1,2-Dibromo-2,4-dicyanobutane (Tectamal 38) Biguanide derivatives such as 1,1'-(Hexamethylene bis[5-(4-chlorophenyl)biguanide]digluconate (chlorhexidine glucuronate) and Bis(p-chlorophenyldiguanide)hexane dihydrochloride (chlorhexidine hydrochloride), Hydantoin derivatives such as 1-Bromo-3-chloro-5,5'-dimethyl hydantoin (dantobrom) and 1,3-Bis-(hydroxymethyl)-5,5'-dimethyl hydantoin (glidant, dantguard), Pyridine derivatives such as sodium pyridine thiol-1-oxide (sodium pyrithione), zinc bis(2-pyridylthio-1-oxide) (zinc pyrithione, zinc omazine, ZPT), 2,3,5,6-Tetrachloro-4-(methylsulphonyl)pyridine (densyl), and copper bis(2-pyridylthio-1-oxide) (copper pyrithione, copper omazine, CuPT), 2-Isopropyl-5-methylphenol (thymol, 2-isopropyl-5-methylphenol), 3-Methyl-4-iso-propylphenol (isopropylmethylphenol, piosol), o-Phenylphenol (OPP, orthophenylphenol), Phenol (phenol, carbolic acid), Butyl-p-hydroxybenzoate (butylparaben), Ethyl-p-hydroxybenzoate (ethylparaben), Methyl-p-hydroxybenzoate (methylparaben), Propyl-p-hydroxybenzoate Phenolic compounds such as e (propylparaben), m-Methylphenol (methacresol), o-Methylphenol (orthocresol), p-Methylphenol (paracresol), o-Phenylsodiumphenoxide (orthophenylphenol sodium), 2-Benzyl-4-chlorophenol (chlorophene), p-Chlorophenol (parachlorophenol), 4-Chloro-3,5-dimethylphenol (parachlorometaxylenol), and 2-Methyl-3-chlorophenol (parachlorometacresol), Phthalimide derivatives such as N-(Fluorodichloromethylthio)-phthalimide (Fluorofolpet, Briventol A3), Peptides such as ε-Poly-L-lysine (polylysine, 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, Polyvinylpyrrolidone iodide (povidone iodine, Isodine), p-Chlorophenyl-3-iodopropagyl formal, and 3-Bromo-2,3-diiodo-2-propenylethylcarbonate (Sampras). Chlorine-based substances such as sodium hypochlorite, sodium dichlorinated isocyanurate, and trichlorinated isocyanuric acid. Peroxide-based substances such as hydrogen peroxide, chlorine dioxide (stabilized chlorine dioxide, Biotalk), and peracetic acid. Metal salts such as copper naphthenate, silver / zirconium phosphate (Novaron AG300), silver chloride / titanium oxide, silver-zinc / calcium phosphate (Silver Ace), silver-zinc / zeolite (silver-zinc aluminosilicate), zinc oxide, silver / zirconium phosphate (Novaron AGZ330), and N-stearoyl-L-glutamic acid AgCu salt (Holonkiller), 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), Oxide-based materials such as ethylene oxide (EO) and propylene oxide (PO), 4,4'-(Tetramethylenedicarbonyldiamino)bis(1-decylpyridinium bromide) (dimer 135), Decyldimethylbenzylammonium chloride (benzalkonium chloride), Didecyldimethylammonium chloride (Bardak 2250 / 80), Diisobutylphenoxyethoxydimethylbenzylammonium chloride (benzothonium chloride, Hyamine 1622), Hexadecyl trimethyl ammonium bromide (cetylammonium bromide, 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 chloride (Bardack 170P), 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 (Duron, DCMU, Briventol A6). Particularly preferred are isothiazoline-based antibacterial and antifungal agents such as 2-n-octyl-4-isothiazolin-3-one (Skaene 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).

[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), and Nn-butyl-1,2-benzisothiazolin-3-one (BBIT) are preferred. These antibacterial and antifungal agents can be used individually or in combination of two or more.

[0212] The amount of antibacterial and antifungal agents 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 in terms of active ingredient concentration relative to the total water-repellent composition, and may also 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 antibacterial and antifungal agents may be 1.5 to 450 ppm, preferably 7.5 to 300 ppm, and particularly preferably 75 to 150 ppm, relative to the total water-repellent composition.

[0213] The amount of 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 relative to the non-fluorine copolymer (A), and may also 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. For example, the amount of antibacterial and antifungal agent may be 4.5 to 1350 ppm, preferably 22.5 to 900 ppm, and particularly preferably 225 to 450 ppm, relative to the non-fluorine copolymer (A).

[0214] The antibacterial and antifungal agents may also be used as the following preservatives or antimicrobial agents.

[0215] (Preservative) Preservatives are mainly used to enhance preservative and bactericidal properties and maintain preservation during long-term storage. Examples of such preservatives include isothiazolinoline-based organosulfur compounds, benzisothiazoline-based organosulfur compounds, benzoic acids, and 2-Bromo-2-nitropropane-1,3-diol. The amount of preservative is preferably 0.0001 to 1% by weight of the total weight of the water-repellent composition. If the amount of preservative is above the lower limit of the above range, the effect of adding the preservative is sufficiently obtained, and if it is below the upper limit, the storage stability of the water-repellent composition is good.

[0216] (Antibacterial agent) Antibacterial agents are components that suppress the growth of bacteria on fibers and also suppress the generation of unpleasant odors derived from microbial decomposition products. Examples of antibacterial agents include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0217] (UV absorber) UV absorbers are chemicals that have the effect of protecting against ultraviolet rays. They absorb ultraviolet rays and convert them into infrared rays, visible light, etc., and release them. Examples of UV absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0218] (Deodorizer) Examples of deodorizers include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (such as the zinc complex of trisodium methylglycinediacetate described in International Publication No. 2012 / 090580).

[0219] (fragrance) While not particularly limited, lists of usable fragrance ingredients can be found in various publications, such as "Perfume and Flavor Chemicals," Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994), "Synthetic Fragrances: Chemistry and Product Knowledge," by Motoichi Indo, Chemical Daily Co. (1996), "Perfume and Flavor Materials of Natural Origin," Steffen Arctander, Allured Pub. Co. (1994), "Encyclopedia of Fragrances," edited by the Japan Fragrance 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), and these are considered part of the disclosures in this specification by citing them.

[0220] (Amount of other ingredients) The amount of 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, per 100 parts by weight of non-fluorine copolymer (A). The amount of 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, per 100 parts by weight of non-fluorine copolymer (A).

[0221] <Method for producing a water-repellent composition> A method for producing a water-repellent composition includes obtaining a non-fluorine copolymer (A) by 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). The water-repellent composition of this disclosure can be obtained by this method (hereinafter referred to as the first method).

[0222] In one embodiment, a method for producing a water-repellent composition includes copolymerizing a hydrophobic monomer (a1) having a hydrocarbon group with 2 to 40 carbon atoms and 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-fluorine copolymer (A). By this method, the water-repellent composition of the present disclosure can be obtained.

[0223] Polymerization methods include, for example, suspension polymerization and emulsion polymerization, and emulsion polymerization is preferred from the viewpoint of obtaining an emulsion of non-fluorine copolymer (A).

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

[0225] The proportion of the surfactant may be, 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, based on 100 parts by weight of the total amount of monomers (specifically, a hydrophobic monomer having a hydrocarbon group having 2 to 40 carbon atoms (a1), at least one chloride monomer selected from the group consisting of vinyl chloride and vinylidene chloride (a2), a cyclic hydrocarbon group-containing monomer added as needed (a3), a crosslinkable monomer added as needed (a4), and other monomers added as needed (a5), and so on).

[0226] The proportion 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, per 100 parts by weight of the total amount of monomers. The liquid medium may be one of those listed above. For example, the liquid medium may be water. In emulsion polymerization, an organic solvent may be added further. As the organic solvent, one of the liquid media listed above may be used. The organic solvent may be a water-soluble glycol-based solvent, for example, ethylene glycol or propylene glycol.

[0227] In emulsion polymerization, the organic acids listed above may be added. For example, the organic acid may be a carboxylic acid such as acetic acid. The amount of 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, or 0.5 parts by weight or less, per 100 parts by weight of the total amount of monomers.

[0228] Next, an emulsifier may be added to this mixture.

[0229] Examples of emulsifiers include well-known emulsifiers such as cationic emulsifiers and anionic emulsifiers.

[0230] Furthermore, the above-mentioned surfactants can also be used as emulsifiers.

[0231] Furthermore, the emulsifier may also contain a reactive emulsifier. When the emulsifier contains a reactive emulsifier, the non-fluorinated copolymer (A) (polymer of the above monomers) becomes a polymer that contains constituent units derived from the reactive emulsifier.

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

[0233] A reactive emulsifier is an emulsifying dispersant having radical reactivity, that is, an emulsifier having one or more polymerizable unsaturated groups in its molecule, and is an emulsifier copolymerizable with the monomers described above. Examples of reactive emulsifiers include the reactive emulsifier described in Japanese Patent Publication No. 2017-25440, and preferably, a reactive emulsifier represented by the following formula. [ka]

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

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

[0236] If the reactive emulsifier is the reactive emulsifier shown in the above formula, the product stability of the aqueous dispersion (water-repellent composition) is improved without reducing water repellency. Examples of the reactive emulsifier represented by the above formula include polyoxyethylene alkylphenols.

[0237] Emulsifiers can be used alone or in combination of two or more types.

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

[0239] Furthermore, the proportion of the emulsifier may be, for example, 8 parts by weight or more, or 20 parts by weight or less, based on 100 parts by weight of the total amount of the isocyanate derivative (B) and the non-fluorine copolymer (A).

[0240] Furthermore, the proportion of the emulsifier may be, for example, 0.5% by weight or more, or for example, 5% by weight or less, relative to the water-repellent composition.

[0241] Then, after mixing the above-mentioned components, the mixture is stirred and subjected to ultrasound to emulsify it.

[0242] As a method of stirring, dispersers such as homomixers, ultrasonic homogenizers, pressurized homogenizers, milders, and porous membrane injection dispersers can be used, and preferably, a homomixer is used.

[0243] The stirring conditions are set as appropriate. When using a homomixer, 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, if a portion of the monomer was added when preparing the above-mentioned mixture, the remainder of the monomer is added to this mixture.

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

[0246] Examples of polymerization initiators 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, azo compounds are used, and more preferably, azobisisobutyronitrile is used.

[0247] The proportion of polymerization initiator may be, for example, 0.01 parts by weight or more, and for example, 10 parts by weight or less, per 100 parts by weight of monomer.

[0248] Furthermore, a chain transfer agent may be added to this mixture as needed.

[0249] Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially alkyl mercaptans (e.g., having 1 to 30 carbon atoms)), inorganic salts such as sodium hypophosphite and sodium bisulfite, and lauryl mercaptan is preferred.

[0250] The proportion 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, per 100 parts by weight of monomer.

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

[0252] The heating conditions include a heating temperature of, for example, 40°C or higher, and for example, 80°C or lower, and a heating time of, for example, 1 hour or more, and for example, 6 hours or less. This yields an emulsion of the non-fluorine copolymer (A), and a water-repellent composition containing the isocyanate derivative (B) and the non-fluorine copolymer (A) (emulsion).

[0253] In the first method, the monomers constituting the non-fluorine copolymer (A) described above are polymerized in the presence of the isocyanate derivative (B). However, the isocyanate derivative (B) can also be added after the monomers have been polymerized (second method). Alternatively, the isocyanate derivative (B) can also be added 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-described production method, except that the monomers constituting the 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 this disclosure.

[0255] Alternatively, the monomer can be polymerized to prepare a non-fluorinated copolymer (A), and then the obtained non-fluorinated copolymer (A) can be blended with an isocyanate derivative (B) (Method 4). Alternatively, the monomer can be polymerized first to prepare a non-fluorinated copolymer (A), and then the obtained non-fluorinated copolymer (A) can be blended with an isocyanate derivative (B), a surfactant, and a liquid medium (Method 5).

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

[0257] When solution polymerization is employed, the monomer is dissolved in an organic solvent in the presence of the polymerization initiator described above, followed by nitrogen purging and heating while stirring.

[0258] The polymerization initiator described above may be used as the polymerization initiator. The blending 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, per 100 parts by weight of monomer.

[0259] Examples of organic solvents include the solvents listed above in the section on liquid media. The organic solvent may be, for example, glycols (e.g., glycols with 2 to 40 carbon atoms, specifically ethylene glycol, propylene glycol, etc.), esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate, butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically ethanol, butanol, isopropyl alcohol). Preferably, a water-soluble glycol-based solvent (e.g., ethylene glycol, propylene glycol, etc.) may be used as the organic solvent.

[0260] The proportion of the organic solvent may be, for example, 10 parts by weight or more, preferably 50 parts by weight or more, or, for example, 2000 parts by weight or less, preferably 1000 parts by weight or less, per 100 parts by weight of the monomer.

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

[0262] As a result, a non-fluorine copolymer (A) is obtained.

[0263] Then, after generating a non-fluorinated copolymer (A) by solution polymerization, the organic solvent is removed, and the non-fluorinated copolymer (A) is combined with an isocyanate derivative (B) in a surfactant and a liquid medium to prepare an emulsion of the non-fluorinated copolymer (A).

[0264] <Uses of water-repellent compositions> Examples of applications for the water-repellent compositions in this disclosure include external treatment agents (surface treatment agents) or internal treatment agents, water repellents (water repellents, oil repellents or water- and oil-repellent agents, etc., especially water repellents), antifouling agents, dirt removal agents, release agents, mold release agents (external mold release agents or internal mold release agents), and the like.

[0265] <Manufacturing method for processed products> The method for manufacturing the processed product in this disclosure includes the step of applying the water-repellent composition of this disclosure to a substrate (particularly a fibrous substrate).

[0266] [Processed Products] Examples of substrates treated with the water-repellent composition of this 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, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Various examples of textile products can be given. For example, natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or blends thereof. An example of a substrate treated with the water-repellent composition will be described in detail regarding woven and knitted fabrics.

[0267] (Woven or knitted fabrics) • Manufacturing methods for knitted fabrics Woven or knitted fabrics can be obtained by weaving or knitting the above-mentioned blended entangled yarn to obtain raw fabric, and then by post-processing and water-repellent treatment. Weaving and knitting can be carried out using known looms and knitting machines, and the preparatory processes preceding weaving and knitting can also be carried out using known equipment.

[0268] Furthermore, in post-processing, the raw fabric is first scouring and relaxed. Scouring and relaxation can be carried out in a continuous or batch manner at a temperature of 80 to 130°C. Usually, it is preferable to carry it out in a batch manner at a temperature of 100°C or lower, and it is particularly preferable to carry it out using a high-pressure liquid-jet dyeing machine equipped with a jet nozzle.

[0269] After scouring and relaxing, the woven or knitted fabrics are pre-set. Pre-setting is typically done using a pin tenter, dry heat treatment at 170-200°C for 30-120 seconds. After pre-setting, the fabrics are dyed according to conventional methods, followed by final setting as needed.

[0270] After post-processing, the woven or knitted fabric may be treated to be water-repellent. For water-repellent treatment, first, an aqueous solution containing a water-repellent agent (which may be a water-repellent agent composition as described herein) is prepared. Next, the aqueous solution is applied to the woven or knitted fabric after the post-processing using a padding method, spray method, slit coater method, etc., and then dry-heat treated at 105 to 190°C for 30 to 150 seconds. The aqueous solution may also contain a crosslinking agent, softener, antistatic agent, etc., as needed. After water-repellent treatment, the woven or knitted fabric may be calendered to further improve its water-repellent performance.

[0271] Woven and knitted fabrics are suitable for clothing applications, particularly for uniforms, women's wear, and sportswear.

[0272] • Laminated fabric The present disclosure may also be provided as a laminated fabric having a breathable waterproof layer on one side of the woven or knitted fabric. The breathable waterproof layer may be directly laminated to the woven or knitted fabric, or it may be laminated to 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 should be positioned so that the woven or knitted fabric side is exposed to rainwater, etc.

[0273] • Breathable waterproof layer A breathable waterproof layer is a layer that covers one side of a woven or knitted fabric, and is formed from a resin that has waterproof and breathable properties.

[0274] The breathable waterproof layer may be formed by directly applying resin (the resin constituting the breathable waterproof layer) to the woven or knitted fabric, or it may be laminated to one side of the woven or knitted fabric via an adhesive layer described later. In this disclosure, a blended entangled yarn having fine protrusions due to loops or slack is used in the woven or knitted fabric. As a result, the protrusions become firmly entangled with the adhesive layer or the breathable waterproof layer, creating an anchoring effect that makes it even more difficult for the woven or knitted fabric and the breathable waterproof layer to separate. 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 anchoring effect may not be sufficiently realized, and in such cases, the woven or knitted fabric and the breathable waterproof layer tend to separate easily.

[0275] The resin constituting the breathable waterproof layer is not particularly limited, but it is preferably composed of polyurethane resin as the main component, for example, it is preferable that polyurethane resin is contained in a proportion of 80% by weight or more. Polyurethane resin is generally suitable for forming a resin layer that has breathability and waterproofing properties. Among these, a microporous type is preferred when considering breathability, but if there is a possibility of being exposed to rain for a long time or repeated use such as washing is expected, a non-porous type of breathable polyurethane may be used instead of a microporous type.

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

[0277] The breathable waterproof layer may have a microporous structure or a non-porous structure. Furthermore, if it has a microporous structure, inorganic fine powder may be incorporated into the breathable waterproof layer to ensure the desired breathability.

[0278] Examples of inorganic fine powders include fine powders made from silicon dioxide, aluminum dioxide, or titanium dioxide. The average primary particle size of the inorganic fine powder is preferably about 7 to 40 nm. The amount of inorganic fine powder is preferably 3 to 50% by weight, and more preferably 5 to 50% by weight, relative to the total amount of the moisture-permeable waterproof layer.

[0279] The thickness of the breathable waterproof layer is preferably 5 μm or more, and more preferably 10 to 30 μm. A thickness within this range provides an excellent balance of waterproofing and breathability, and also offers advantages in terms of texture and tear strength.

[0280] ·Adhesive layer The laminated fabric preferably includes an adhesive layer. In other words, it is preferable that the woven or knitted fabric and the breathable waterproof layer are laminated via an adhesive layer. The reason for this is explained below. In this disclosure, as the woven or knitted fabric, as described above, a fabric having fine protrusions on its surface due to loops or slack is used. Therefore, the protrusions become firmly intertwined with the adhesive layer, creating an anchoring effect, which makes it even more difficult for the woven or knitted fabric and the breathable waterproof layer to separate.

[0281] Furthermore, when a breathable waterproof layer is directly laminated onto the woven or knitted fabric, for example by a coating method, protrusions on the surface of the woven or knitted fabric may penetrate the breathable waterproof layer, resulting in the formation of pinholes and inferior water resistance and strength. There is also a concern that the coating may not be uniform, leading to uneven thickness in the breathable waterproof layer. To prevent this, if the surface of the woven or knitted fabric is smoothed by calendering, for example, the protrusions or air-retaining layer may be reduced, which may decrease water repellency. Therefore, in this disclosure, it is preferable that the woven or knitted fabric and the breathable waterproof layer are laminated with an adhesive layer in between.

[0282] The type of adhesive that constitutes the adhesive layer is not particularly limited, but it is preferable that it has excellent compatibility with the breathable waterproof layer. For example, if a resin mainly composed of polyurethane resin is selected as the resin that constitutes the breathable waterproof layer, it is preferable to use an adhesive layer made of polyurethane adhesive. The polyurethane adhesive may be of any structure, such as ether-based, ester-based, or polycarbonate-based, but from the viewpoint of providing excellent breathability, ether-based adhesives are preferred.

[0283] The adhesive layer may be formed over the entire surface of one side of the woven or knitted fabric, or it may be formed in a pattern from the viewpoint of breathability or texture. The pattern is not particularly limited, but examples include dots, lines, grids, checkerboard patterns, tortoiseshell patterns, etc., and it is preferable that they are uniformly arranged throughout.

[0284] The adhesive layer thickness is preferably around 10 to 100 μm, and more preferably 20 to 80 μm. If the thickness is less than 10 μm, it is difficult to obtain a durable laminated fabric even if the adhesive occupies a large area, and if it exceeds 100 μm, the manufacturing cost increases and further adhesion cannot be expected, so neither is desirable.

[0285] • Lining fabric In the laminated fabric of this disclosure, a lining fiber fabric may be laminated on the breathable waterproof layer (on the side of the breathable waterproof layer opposite to the side on which the woven or knitted fabric of this disclosure is laminated). The lining fiber fabric can protect the breathable waterproof layer, making it possible to further improve the waterproofness (water pressure resistance) and strength. In addition, by laminating the lining fiber fabric, the elongation of the entire laminated fabric can be suppressed, so that the protrusions of the blended composite yarn are not reduced as a result of being pulled by the elongation of the woven or knitted fabric due to the finishing process after lamination or tension during wear, and the above water repellency can be maintained at a higher level. Furthermore, when a lining fiber fabric is laminated, the water repellency can be further improved.

[0286] Examples of lining fabrics include various woven and knitted fabrics. Among these, knitted fabrics are preferable because, compared to woven fabrics, the constituent threads tend to protrude more easily from the surface, resulting in a less flat surface, which allows for a better anchoring effect and makes it less likely to peel off from the breathable waterproof layer. In particular, tricot knitted fabric is preferable because, compared to knitted fabrics with other structures, its elasticity is suppressed, so the gaps between the stitches do not become too large, and water repellency is more effectively expressed. Furthermore, tricot knitted fabric is also preferable because it can be made into a long piece of fabric during the knitting process, resulting in fewer seams, and can be uniformly laminated on the breathable waterproof layer.

[0287] The material of the fibers constituting the lining fabric is not particularly limited and can be selected as appropriate, but nylon fibers are preferred. This is because, since acid dyes are generally used for nylon fibers, the migration and sublimation of disperse dyes to the breathable waterproof layer, which is a problem with polyester fibers and the like that use disperse dyes, is less likely to occur. The form (long fibers, short fibers, or spun yarn) or fineness of the constituent fibers of the lining fabric is not particularly limited and can be selected as appropriate within a range that does not impair the effects of this disclosure.

[0288] • Characteristics of laminated fabric The laminated fabric has excellent waterproofing properties. A preferred example of the waterproofing properties of the laminated fabric of this disclosure is a water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method), which is, for example, 10,000 mm or more, preferably 15,000 mm or more, more preferably 16,000 mm or more, and particularly preferably 20,000 mm or more. There is no particular limit to the upper limit of the water level, but examples include 50,000 mm or 25,000 mm.

[0289] Laminated fabrics have excellent moisture permeability. A preferred example of the moisture permeability of the laminated fabrics of this disclosure is a moisture permeability of, for example, 10,000 g / m² as measured according to the JIS L 1099:2012 B-1 method (potassium acetate method). 2 24 hours or more, preferably 15,000 g / m² 2 24 hours or more, more preferably 20,000 g / m² 2 • 24 hours or more is a possible example. There are no particular restrictions on the upper limit of this moisture permeability, but for example, 40,000 g / m 2 24h or 35,000g / m² 2 • 24h • mm is one example.

[0290] In the laminated fabric, delamination between the woven / knitted fabric and the breathable waterproof layer is suppressed. In the laminated fabric of this disclosure, a suitable example of the peel strength between the woven / knitted fabric and the breathable waterproof layer is, for example, 5 N / 2.54 cm or more, preferably 5 to 50 N / 2.54 cm, more preferably 6 to 30 N / 2.54 cm, and particularly preferably 9 to 25 N / 2.54 cm, as measured according to the method of JIS L 1089. To achieve the peel strength within the above range, for example, a woven / knitted fabric that has not been calendered can be used, or an adhesive layer can be provided.

[0291] • Manufacturing method of laminated fabric The method for manufacturing the laminated fabric is not particularly limited, but examples include the first and second manufacturing methods shown below. First manufacturing method: Includes the step of forming the moisture-permeable waterproof layer by applying the resin constituting the moisture-permeable waterproof layer to the surface of a woven or knitted fabric. A second manufacturing method includes the steps of forming an adhesive layer on a woven or knitted fabric or a breathable waterproof layer, and bonding the woven or knitted fabric and the breathable waterproof layer via the adhesive layer.

[0292] It is preferable to maintain as many protrusions as possible on the surface of the woven or knitted fabric used in the laminated fabric (i.e., the woven or knitted fabric of the present disclosure described above). For example, if calendering is applied to the woven or knitted fabric to facilitate coating or other processes, the fine protrusions of the blended entangled yarns may be flattened, resulting in a flat surface, and it may not be possible to achieve a specific water droplet rolling angle. Furthermore, if calendering is applied, it may not be possible to sufficiently maintain the above-mentioned air-retaining layer, and the desired water repellency may not be achieved. Therefore, it is preferable to carefully consider the conditions for calendering. For example, when calendering a woven or knitted fabric, it is advisable to use normal conditions (e.g., a temperature of 130°C or higher and a linear pressure of 200 to 20000 N / cm) that do not reduce the protrusions of the blended entangled yarns too much. Note that calendering may also be performed without heating.

[0293] In the first manufacturing method, a coating method can be used to apply the resin constituting the moisture-permeable waterproof layer to the surface of the woven or knitted fabric. In the coating method, a knife coater or a comma coater can be used. Furthermore, 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, a lamination method is used as a method for forming an adhesive layer on a woven or knitted fabric or a breathable waterproof layer. In the lamination method, a resin solution or a hot melt method can be used to form the adhesive layer. First, a resin composition for forming a breathable waterproof layer (for example, a resin composition containing a resin and an organic solvent) is applied to the surface of a release agent (release paper, release cloth, or release film, etc.) with a clearance, and the breathable waterproof layer is formed while adjusting the thickness. The mixture is then heat-treated to allow it to react completely and obtain a film. The release agent can be removed as appropriate after lamination or curing.

[0295] Then, an adhesive layer is formed on the woven or knitted fabric or the breathable waterproof layer. For example, if 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 to the entire surface or in a pattern. After drying, an adhesive layer is formed, and the woven or knitted fabric and the breathable waterproof layer are bonded together via the adhesive layer, and the second manufacturing method can be carried out by pressing or heat-pressing the two together.

[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 in practical terms, it is more preferable to use one that melts in a temperature range of about 80 to 150°C. In this case, first, the hot melt resin is melted while considering 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 allowed to mature while cooling at room temperature to form an adhesive layer. After that, 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 a breathable waterproof layer is laminated using a coating method, there is a concern that pinholes may occur in the breathable waterproof layer due to fine protrusions on the surface of the woven or knitted fabric, which tends to reduce water pressure resistance. Furthermore, when calendering is applied to the woven or knitted fabric in an attempt to form a uniform breathable waterproof layer, there is a concern that the protrusions or air-retaining layer will be reduced, making it impossible to achieve the desired water repellency, and further scrutiny of the calendering conditions will be necessary, which may make the process itself complicated.

[0298] Subsequently, a lining fabric can be laminated onto the breathable waterproof layer using a known and appropriate method.

[0299] • Uses of laminated fabrics Laminated fabrics offer excellent water repellency and breathable waterproofing, and the breathable waterproof layer does not peel off even in harsh environments, making them suitable for use in fields such as uniforms, sportswear, and outdoor products used outdoors.

[0300] [Processing method] The water-repellent composition of this disclosure can be applied to a substrate by conventionally known methods as a treatment agent (particularly a surface treatment agent). The water-repellent composition of this disclosure may be diluted by dispersing it in an organic solvent or water as needed, and then applied to the surface of the substrate by known methods such as immersion coating, spray coating, foam coating, etc., and dried. After drying, a textile product with the solid components of the water-repellent composition attached is obtained. If necessary, it may also be applied together with a suitable crosslinking agent and cured. Furthermore, the water-repellent composition of this disclosure can be used in combination with various additives such as water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle-preventing agents, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, insecticides, and defoaming agents. Examples of various additives may be the same as those described in "other components" in the water-repellent composition described above. The concentration of the non-fluorine copolymer (A) in the treatment agent that comes into contact with the substrate may be changed as appropriate depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0301] [Textile products] Various examples of textile products can be given as base materials, such as cloth products and paper products. Textile products that serve as base materials are also called textile base materials.

[0302] Examples of textile products include natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or blends thereof. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as fabrics and carpets. However, treatment may also be applied to fibers, yarns, and intermediate fiber products (e.g., slivers or rovings) before they are made into fabric.

[0303] Examples of paper products include paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as crushed wood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine, recycled corrugated cardboard or deinked paper, paper containers, and molded products made from paper. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-grade paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive 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 textile products (e.g., cloth) by any known method for treating textile products with a liquid. The textile product may be immersed in the water-repellent composition, or the solution may be applied to or sprayed onto the textile product. The treated textile product is preferably dried and cured by heating to exhibit 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. Good performance can also be obtained with low-temperature heating (e.g., 100°C to 140°C) in this disclosure. The heating time may be 5 seconds to 60 minutes in this disclosure, for example, 30 seconds to 3 minutes.

[0305] Alternatively, the water-repellent composition may be applied to textile products by cleaning methods, for example, by washing or dry cleaning.

[0306] The textile products to be treated may be cloths, including woven fabrics, knitted fabrics and nonwoven fabrics, cloths in the form of clothing and carpets, but may also be fibers or yarns or intermediate textile products (e.g., slivers or rovings). The water-repellent compositions of this disclosure are particularly effective in making textile products (e.g., synthetic fibers) water-repellent.

[0307] The fibers that make up the textile product may be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, or inorganic fibers. Fibers may be used individually or in combination of two or more types.

[0308] Examples of natural fibers include cellulose fibers such as cotton, flax, and pulp, as well as chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as groundwood pulp (GP), pressured groundwood 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); recycled paper pulp such as deinking pulp (DIP) and waste pulp (WP), and semi-chemical pulp (CP).

[0309] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymerized polyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; and polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupro, polynosic rayon, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0310] Alternatively, the textile product may be leather. The manufacturing polymer may be applied to the leather in the form of an aqueous solution or aqueous emulsion at various stages of leather processing, for example, during the wetting process or during the finishing process, in order to make the leather hydrophobic and oleophobic. Alternatively, the textile product may be paper. The manufacturing polymer may be applied to pre-formed paper, or it may be applied at various stages of papermaking, for example, during the drying period of the paper.

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

[0312] [Pretreatment of textile products] Textile products may be pre-treated before being treated with the water-repellent composition of this disclosure. Pre-treating the textile products can impart excellent fastness to the textile products after treatment with the water-repellent composition.

[0313] Examples of pretreatments for textile products include cationization by reaction with reactive quaternary ammonium salts, anionization by sulfonation, carboxylation, phosphorylation, etc., acetylation, benzoylation, carboxymethylation, grafting, tannic acid treatment, and polymer coating after anionization.

[0314] The method for pre-treating textile products is not limited, but conventionally known methods can be used. This may involve dispersing and diluting the pre-treatment solution in an organic solvent or water as needed, applying it to the surface of the textile product by known methods such as immersion coating, spray coating, or foam coating, and then drying it. The pH and temperature of the pre-treatment solution may be adjusted according to the desired degree of treatment. As an example of a method for pre-treating textile products, a method of pre-treating textile products with a hydrocarbon-based water repellent will be described in detail.

[0315] The pretreatment method for textile products involves applying -SO3M to the fibers. 1 (In the formula, M 1 (represents a monovalent cation) a monovalent group represented by -COOM 2 (In the formula, M 2 A monovalent group represented by (where is a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X1 and X 2 The process may include a step of adding at least one functional group (hereinafter sometimes referred to as a "specific functional group") selected from the group consisting of monovalent groups (each independently representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

[0316] M 1 Examples include H, K, Na, or ammonium ions which may have substituents. 2 Examples include H, K, Na, or ammonium ions which may have substituents. 1 or X 2 If it 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] Fibers containing the above-mentioned 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 above-mentioned specific functional group is attached to the fiber material. The attachment of the compound may be such that a portion of the compound and a portion of the fiber are chemically bonded, to the extent that a sufficient amount of the above-mentioned specific functional group remains. (ii) Prepare a fiber in which the above-mentioned specific functional group is directly introduced into the material constituting the fiber.

[0318] (i) For example, a functional group-containing fiber can be obtained by a functional group introduction step in which the fiber material is treated with a pretreatment solution containing one or more compounds having the above-mentioned specific functional group.

[0319] There are no particular restrictions on the material of the fiber material, and examples include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene; and composite fibers and blended fibers thereof. The fiber material may take any form, such as fibers (tow, sliver, etc.), yarn, knitted fabrics (including interwoven fabrics), woven fabrics (including interwoven fabrics), nonwoven fabrics, and paper.

[0320] In this embodiment, from the viewpoint of obtaining good water repellency in the resulting textile product, it is preferable to use a fiber material containing polyamide and polyester as a base material. In particular, it is preferable to use nylon such as nylon 6 and nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.

[0321] The above -SO3M 1 As a compound having this property, phenolic polymers can be used. Examples of such phenolic polymers include those containing at least one compound represented by the following general formula.

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

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

[0324] The above M 3 Examples include H, K, Na, or ammonium ions which may have substituents.

[0325] The above M 4 Examples include H, K, Na, or ammonium ions which may have substituents.

[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] The above-COOM 2 Examples of compounds having this property include polycarboxylic acid polymers.

[0328] As polycarboxylic acid polymers, for example, polymers synthesized by conventionally known radical polymerization methods using acrylic acid, methacrylic acid, maleic acid, etc. as monomers, or commercially available polymers can be used.

[0329] One method for producing polycarboxylic acid polymers is to add a radical polymerization initiator to an aqueous solution of the monomer and / or its salt, and heat the reaction at 30 to 150°C for 2 to 5 hours. At this time, alcohols such as methanol, ethanol, isopropyl alcohol, or aqueous solvents such as acetone may be added to the aqueous solution of the monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators using combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo 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 to adjust the degree of polymerization.

[0330] In radical polymerization, copolymerizable monomers can be used in addition to the monomers mentioned above. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, as well as acrylamide, acrylates, and methacrylates. Acrylates and methacrylates are preferably those having a hydrocarbon group with 1 to 3 carbon atoms, which may have substituents such as hydroxyl groups. 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 individually or in combination of two or more.

[0331] The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized by alkali metals or amine compounds. Examples of alkali metals include sodium, potassium, and lithium, while examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

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

[0333] For polycarboxylic acid polymers, commercially available products such as "NeoCrystal 770" (manufactured by Nikka Chemical Co., Ltd., product name) and "Cellopol PC-300" (manufactured by Sanyo Chemical Industries, Ltd., product name) can be used.

[0334] The above - OP(O)(OX 1 )(OX 2 Examples of compounds having the following general formula include phosphate ester compounds. [ka] [where, X 1 or X 2 This is synonymous with the above, X 3 This represents an alkyl group with 1 to 22 carbon atoms.

[0335] As the phosphate ester compounds mentioned above, phosphate monoesters, diesters, and triesters in which the alkyl ester portion has an alkyl group having 1 to 22 carbon atoms, as well as mixtures thereof, can be used.

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

[0337] For the phosphate ester compound, commercially available products such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name) can be used.

[0338] The pretreatment solution containing one or more compounds having the above-mentioned specific functional groups can, for example, be an aqueous solution of the compounds described above. The pretreatment solution may also contain acids, alkalis, surfactants, chelating agents, etc.

[0339] Methods for treating fibrous materials with the above-mentioned pretreatment solution include, for example, padding, immersion, spraying, and coating. For padding, for example, methods using padding equipment described on pages 396-397 of the Dictionary of Textile Dyeing and Processing (published in 1963 by Nikkan Kogyo Shimbun) and pages 256-260 of Color Dyeing Chemistry III (published in 1975 by Jikkyo Shuppan Co., Ltd.) can be used. For coating, for example, methods using coating machines described on pages 473-477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used. For immersion, for example, methods using batch-type dyeing machines described on pages 196-247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used, and liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, cheese dyeing machines, etc. can be used. Examples of spray treatments include air sprays that atomize the treatment solution using compressed air, and air sprays that use a hydraulic atomization system. The concentration of the treatment solution and the treatment conditions such as heat treatment after application can be adjusted as appropriate, taking into account the purpose, performance, and other conditions. If the pretreatment solution contains water, it is preferable to dry it to remove the water after it has been applied to the fiber material. There are no particular restrictions on the drying method, and either a dry heat method or a wet heat method may be used. There are no particular restrictions on the drying temperature, but for example, drying at room temperature to 200°C for 10 seconds to several days is sufficient. If necessary, after drying, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes.

[0340] Furthermore, if the fiber material is to be dyed, the pretreatment with the pretreatment solution may be performed before dyeing or in the same bath as the dyeing. However, if reducing soaping is performed, there is a risk that the compounds having the specific functional groups (e.g., phenolic polymer compounds, etc.) that have been adsorbed during the process may be removed. Therefore, it is preferable to perform the pretreatment after reducing soaping following dyeing.

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

[0342] In the functional group introduction step using the pretreatment solution, it is preferable to treat the material in such an amount that the amount of compound having the specified functional group attached is 1.0 to 7.0 parts by weight per 100 parts by weight of the fiber material. Within this range, a high level of both durable water repellency and texture can be achieved.

[0343] The pretreatment solution is preferably adjusted to a pH of 3-5. pH adjustment can be done using pH adjusting agents such as acetic acid or malic acid.

[0344] The pretreatment solution may also contain salt to effectively adsorb the compound having the above-mentioned specific functional group onto the fiber material through a salting-out effect. Examples of salts that can be used include sodium chloride. Examples include sodium carbonate, ammonium sulfate, and sodium sulfate.

[0345] In the functional group introduction step using a pretreatment solution, it is preferable to remove any compounds having the specified functional groups that have been excessively treated. One method of removal is washing with water. By ensuring sufficient removal, it is possible to suppress the inhibition of water repellency development in the subsequent water-repellent treatment, and in addition, the texture of the resulting textile product will be improved. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fibers before contacting them with a hydrocarbon-based water repellent.

[0346] (ii) Examples of fibers in which the above-mentioned specific functional groups are directly introduced into the material constituting the fiber include cationic dyeable polyester (CD-PET).

[0347] From the viewpoint of obtaining good water repellency in the resulting textile product, the functional group-containing fibers preferably have a surface zeta potential of -100 to -0.1 mV, and more preferably -50 to -1 mV. The surface zeta potential of the fibers can be measured, for example, using the zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0348] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0349] Examples of the present disclosure are described below, but these examples are not intended to limit the present disclosure.

[0350] [Water repellency test] The water repellency of the test treated fabric was evaluated according to the spray method of JIS-L-1092 (AATCC-22). Water repellency was evaluated according to the following criteria. A higher score indicates better water repellency.

[0351] 100 No wetting or water droplet adhesion was observed on the surface. 90 The surface did not become wet, but the adhesion of small water droplets was observed. 80 Wetting was observed on the surface in the form of small, individual water droplets. 70. Wetness was observed on half of the surface, and small, individual wet spots were seen penetrating the fabric. 50 Wetting was observed across the entire surface. 0. Wetting was observed throughout both the front and back surfaces.

[0352] [Slippery] The test fabric was subjected to warp thread slippage under a load of 160N in accordance with ISO 13936-2, and the seam slippage (mm) was measured. A smaller seam slippage value indicates superior slip resistance.

[0353] [Preparation of raw materials] (Example of production of an aqueous dispersion containing acrylic polymer) Manufacturing Example 1 In a 500 ml plastic container, 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 cationic emulsifier, and 6 g of polyoxyethylene alkyl ether were charged. The mixture was heated to 80°C, stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed using ultrasound for 15 minutes. Next, this mixture was transferred to a 500 ml autoclave, and after nitrogen purging, 0.2 g of lauryl mercaptan was added as a chain transfer agent, and 1.8 g of vinyl chloride was added as a copolymerizable monomer. 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 acrylic polymer (hydrocarbon-based water-repellent resin). This dispersion was further diluted with pure water to prepare an aqueous dispersion of hydrocarbon-based water-repellent resin with a solid content of 30% (more specifically, an aqueous dispersion containing hydrocarbon-based water-repellent resin, surfactant, and liquid medium).

[0354] Manufacturing Examples 2-7 An aqueous dispersion containing an acrylic polymer, a surfactant, and a liquid medium was prepared in the same manner as in Production Example 1, except that the formulation was changed according to Table 1.

[0355] [Table 1]

[0356] (Example of manufacturing a polyurethane-containing aqueous dispersion) Manufacturing Example 8 1. Synthesis of aliphatic polyisocyanate derivatives In a reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser, under a nitrogen atmosphere, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, trade name: Takenate 700), 0.25 parts by mass of 2,6-di(tert-butyl)-4-methylphenol (also known as dibutylhydroxytoluene, BHT, hindered phenol antioxidant), and 0.25 parts by mass of tetraphenyl-dipropylene glycol-diphosphite (organic phosphite ester, co-catalyst) were mixed. Then, 10.7 parts by mass of 1,3-butanediol was added to this mixture, and nitrogen was introduced into the liquid phase for 1 hour. Subsequently, the mixture was heated to 80°C and reacted for 3 hours, after which it was cooled to 60°C. Then, 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium·2-ethylhexanoate was added as an isocyanuration catalyst, and the reaction was carried out for 1.5 hours. Subsequently, 0.04 parts by mass of o-toluenesulfonamide was added to 100 parts by mass of HDI. This reaction mixture was then passed through a thin-film distillation apparatus (temperature 150°C, vacuum 93.3 Pa) and distilled until the remaining HDI monomer content was 0.5% or less, yielding an aliphatic polyisocyanate derivative (an isocyanurate derivative of hexamethylene diisocyanate). The obtained aliphatic polyisocyanate derivative had an isocyanate group content of 20.9% and an average isocyanate functional group count of 3.0.

[0357] 2. Manufacturing of hydrocarbon-based polyurethanes In a reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 100.20 g of the aliphatic polyisocyanate derivative, 67.60 g of Calcol 8098 (stearyl alcohol, manufactured by Kao Corporation) and 22.30 g of oleic alcohol were mixed and reacted under a nitrogen atmosphere at 110°C for 4 hours until the concentration of isocyanate groups reached 3.67%. Next, the reaction solution was cooled to 80°C, and 9.90 g of N-methyldiethanolamine was added as a cationic active hydrogen compound. The reaction was then carried out 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 the disappearance of the isocyanate group could be confirmed by infrared absorption spectroscopy. Next, 57.69 g of methyl erketone was added to the reaction mixture, the temperature was raised to 80°C, and the mixture was stirred until the reaction mixture was completely dissolved, after which it was cooled to 75°C. Subsequently, 18.96 g of acetic acid was added as an acid compound to neutralize the solution. Next, while maintaining the reaction solution at 75°C, 800.0g of deionized water heated to 70°C was gradually added to emulsify (internal emulsification). Next, the solvent was removed using an evaporator under reduced pressure at a water bath temperature of 60°C until the solid content concentration reached 20% by weight or more. Next, an aqueous dispersion containing polyurethane was obtained by adjusting the solid content concentration, excluding acid compounds (acetic acid), with deionized water to 20% by weight.

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

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

[0360] (Example of manufacturing a silicone-containing aqueous dispersion) Manufacturing Example 11 A 200 mL four-necked flask equipped with a stirring rod, thermometer, and reflux tube was charged with 12 g of methyl hydrogen silicone oil (SiH:SiCH3 molar ratio = 50:50 as measured by 1H NMR) and 0.02 g of platinum catalyst. Next, 36 g of 1-hexacocene was placed in a dropping funnel and added dropwise from the dropping funnel while maintaining the temperature at 70°C. After the addition was complete, the reaction was continued at 70°C for 3 hours. The disappearance of the SiH peak was confirmed by infrared spectroscopy (IR), yielding 47 g of solid silicone polymer. Next, 28 g of silicone polymer, 5.6 g of water-soluble glycol solvent, 60 g of pure water, 1.7 g of sorbitan fatty acid ester, 0.7 g of polyoxyethylene alkyl ether, and 0.6 g of cationic emulsifier were placed in a 250 ml glass container, heated to 75°C, stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed using ultrasound for 10 minutes to obtain an aqueous dispersion of silicone polymer. Then, pure water was added to prepare an aqueous dispersion of silicone polymer with a solid content concentration of 30% by weight.

[0361] (Example of manufacturing a wax-containing aqueous dispersion) Manufacturing Example 12 A pressure reaction vessel was sealed and filled with 150g of paraffin wax (melting point 75°C), 350g of pure water, 4.5g of polyoxyethylene alkyl ether, and 3g of sorbitan fatty acid ester. The mixture was heated to 110-120°C while stirring, and then emulsified under high pressure for 30 minutes to prepare an aqueous dispersion of wax. Subsequently, pure water was added to prepare an aqueous dispersion of wax with a solid content of 30% by weight.

[0362] Manufacturing Example 13 150 g of oxidized polypropylene wax with a melting point of 150°C, an acid value of 44 mg KOH / g, and a density of 0.93, 325 g of deionized water, 25 g of a surfactant with an HLB of 15, and 5 g of a 48% potassium hydroxide aqueous solution were placed in a reaction vessel and sealed. The mixture was heated to 160°C while stirring, then emulsified under high pressure for 1 hour, and finally cooled to 90°C to obtain an aqueous dispersion of polypropylene wax. Subsequently, pure water was added to prepare an aqueous dispersion of polypropylene wax with a solid content of 30% by weight.

[0363] [Examples 1-11, Comparative Examples 1-4] The aqueous dispersion described above was mixed with hydrophilic particles (average primary particle size 25 nm, zeta potential +45 mV, turbidity 2.0 ppm) shown in Table 2 to obtain an aqueous dispersion with a solid content 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 solution with a solid content of 1.0 wt%. Next, test cloths (polyester fabric, nylon fabric) were impregnated with this test solution, passed through a mangle, and the test cloths were passed through a pin tenter at 160°C for 1 minute, dried, and cured before performing the test described above.

[0364] [Example 12] The aqueous dispersion described above was mixed with the antibacterial and antifungal agents shown in Table 2 (75 ppm benzisothiazolin-3-one, and a mixture of 5-chloro-2-methyl-2H-isothiazol-3-one and 2-methyl-2H-isothiazol-3-one (weight ratio 3:1) 75 ppm) to obtain an aqueous dispersion with a solid content 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 solution with a solid content of 1.0% by weight. Next, test cloths (polyester fabric, nylon fabric) were impregnated with this test solution, 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-described test was performed.

[0365] [Table 2]

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

Claims

1. The non-fluorinated copolymer (A) comprises repeating units derived from a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms, and repeating units derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride. A water-repellent composition in which, in the non-fluorine copolymer (A), the amount of repeating units derived from the monomer (a2) is 1 to 9% by weight of the sum of the amount of repeating units derived from the monomer (a1) and the amount of 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) is given by formula: CH ２ =C(-R １２ )-C(=O)-Y １１ -(R １１ ) ｋ [In the formula, R １１ It 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 divalent to tetravalent group having 1 carbon atom and directly bonded, -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), and is a divalent to tetravalent group composed of at least one or more selected therefrom, k is between 1 and 3. The water-repellent composition according to claim 1, wherein the compound is represented by [the compound shown].

4. A water-repellent composition according to claim 1, comprising 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-fluorine copolymer (A).

6. The water-repellent composition according to claim 1, wherein in the non-fluorine copolymer (A), the amount of repeating units derived from the monomer (a2) is 3 to 7% by weight of the sum of the amount of repeating units derived from the monomer (a1) and the amount of 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-fluorine copolymer (A).

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

12. The hydrophobic monomer (a1) is given by formula: CH ２ =C(-R １２ )-C(=O)-Y １１ -(R １１ ) ｋ [In the formula, R １１ It 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 Direct bond, divalent to tetravalent, carbon-1 hydrocarbon group, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ A divalent to tetravalent group composed of at least one selected from - and -NR'- (where R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), k is between 1 and 3. It is a compound represented by, The water-repellent composition according to claim 1, wherein in the non-fluorine copolymer (A), the amount of repeating units derived from the monomer (a2) is 3 to 7% by weight of the sum of the amount of repeating units derived from the monomer (a1) and the amount of repeating units derived from the monomer (a2).

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

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

15. Before applying the water-repellent composition to the fiber substrate, the fibers -SO ３ M １ (In the formula, M １ A monovalent group represented by (where indicates a monovalent cation), - COOM ２ (In the formula, M ２ (represents a monovalent cation) and a monovalent group represented by, -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ A method for producing a textile product according to claim 14, comprising the step of imparting one or more functional groups selected from the group consisting of monovalent groups (each independently representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

16. A textile product to which the non-fluorine copolymer (A) in the water-repellent composition according to any one of claims 1 to 13 is attached.

17. -SO ３ M １ (In the formula, M １ A monovalent group represented by (where indicates a monovalent cation), - COOM ２ (In the formula, M ２ (represents a monovalent cation) and a monovalent group represented by, -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ The textile product according to claim 16, wherein a compound having one or more functional groups selected from the group consisting of monovalent groups (each independently representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) is attached to it.

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