Water repellent composition

Abstract

Provided is a water repellent composition containing: a non-fluorinated copolymer (A) containing a repeating unit derived from a hydrophobic monomer (a1) having a C2-40 hydrocarbon group and a repeating unit derived from a chloride monomer (a2) being at least one type selected from the group consisting of vinyl chloride and vinylidene chloride; and an isocyanate derivative (B). In the non-fluorocopolymer (A), the amount of a repeating unit derived from the monomer (a2) is 1-15 wt% with respect to the total of the amount of the repeating unit derived from the monomer (a1) and the content of the repeating unit derived from the monomer (a2).

Description

TECHNICAL FIELD

[0001] The present application relates to a water repellent agent composition. BACKGROUND

[0002] Development of non-fluorine water repellent agents has been made as water repellent agents for imparting water repellency to a base (particularly, a fiber product).

[0003] PRIOR ART DOCUMENTS PATENT DOCUMENTS Patent Document 1: International Publication No. 2021 / 132172 Patent Document 2: Japanese Patent Application Publication No. 2020-189980 SUMMARY

[0004] PROBLEMS TO BE SOLVED BY THE INVENTION When an existing water repellent agent is applied to a fiber product, there is a risk of thread slippage (i.e., slippage), leading to a decrease in reliability as a fiber product.

[0005] An object of the present application is to provide a water repellent agent composition capable of imparting both good water repellency and good slippage resistance to a fiber product.

[0006] TECHNICAL SOLUTION FOR SOLVING THE PROBLEMS The present application includes the following modes.

[0007] [Item 1] A water repellent agent composition comprising: a non-fluorine copolymer (A) containing a repeating unit derived from a hydrophobic monomer (a1) and a repeating unit derived from a chloride monomer (a2), wherein the monomer (a1) has a hydrocarbon group having 2 to 40 carbon atoms, and the monomer (a2) is at least one selected from the group consisting of vinyl chloride and vinylidene chloride; and an isocyanate derivative (B), In the non-fluorine copolymer (A), the amount of the repeating unit derived from the monomer (a2) is 1 to 15% by weight, relative to the total of the amount of the repeating unit derived from the monomer (a1) and the amount of the repeating unit derived from the monomer (a2).

[0008] [Item 2] The water repellent agent composition according to Item 1, wherein the hydrocarbon group in the hydrophobic monomer (a1) is a linear alkyl group having 10 or more carbon atoms.

[0009] [Item 3] The water repellent agent composition according to Item 1 or 2, wherein the hydrophobic monomer (a1) is a compound represented by the formula: 12 CH2=C(-R 11 ) 11 k ​​

[0010] [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 bond, a 1-valent hydrocarbon group having 1 to 4 carbon atoms, a 2- to 4-valent group composed of at least one or more selected from the group consisting of -C6H4-, -0-, -C(=0)-, -S(=0)2-, and -NR'- (R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), k is 1 to 3. [Clause 4] The water repellent agent composition according to any one of clauses 1 to 3, wherein the isocyanate derivative (B) has an alkyl group having 12 or more and 30 or less carbon atoms.

[0011] [Clause 5] The water repellent agent composition according to any one of clauses 1 to 4, wherein the isocyanate derivative (B) is a polyurethane.

[0012] [Clause 6] The water repellent agent composition according to any one of clauses 1 to 5, wherein the isocyanate derivative (B) is a compound obtained by reacting a reactive hydrogen compound with a raw material isocyanate, the reactive hydrogen compound being at least one selected from the group consisting of a hydrocarbon-based alcohol, a sugar alcohol modifier, and a hydroxy acid modifier, and the raw material isocyanate being at least one selected from the group consisting of acyclic aliphatic polyisocyanate and a derivative thereof.

[0013] [Clause 7] The water repellent agent composition according to any one of clauses 1 to 6, which contains a silicone.

[0014] [Clause 8] The water repellent agent composition according to any one of clauses 7, wherein the amount of the silicone is 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the non-fluorinated copolymer (A).

[0015] [Clause 9] The water repellent agent composition according to any one of clauses 1 to 8, wherein, in the non-fluorinated copolymer (A), the amount of the repeating unit derived from the monomer (a2) is 1 to 9% by weight with respect to the total amount of the amount of the repeating unit derived from the monomer (al) and the amount of the repeating unit derived from the monomer (a2).

[0016] [Clause 10] The water repellent agent composition according to any one of clauses 1 to 9, wherein the amount of the isocyanate derivative (B) is 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the non-fluorinated copolymer (A).

[0017] [Clause 11] The water repellent agent composition according to clause 1, wherein, the hydrophobic monomer (al) is a formula: CH2=C(-R12 ) -C(=O)-Y 11 - (R 11 ) k the compound represented by the formula: [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 bond, a 1-valent hydrocarbon group having 1 to 4 carbon atoms, a 2- to 4-valent group composed of at least one or more selected from the group consisting of -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. The isocyanate derivative (B) is a compound having an alkyl group having 12 or more and 30 or less carbon atoms, and obtained by reacting a reactive hydrogen compound with a starting isocyanate, the reactive hydrogen compound being at least one selected from the group consisting of a hydrocarbon group alcohol, a sugar alcohol modifier, and a hydroxy acid modifier, and the starting isocyanate being at least one selected from the group consisting of an acyclic aliphatic polyisocyanate and a derivative thereof, The amount of the isocyanate derivative (B) is 0.1 to 20 parts by weight, relative to 100 parts by weight of the non-fluorine copolymer (A).

[0018] [Item 12] The water repellent agent composition according to Item 1, wherein The hydrophobic monomer (al) is a compound represented by the formula: 11 - R 11 the compound represented by the formula: [In the formula, R 11 is an alkyl group having 12 or more and 25 or less carbon atoms, Y 11 is -O- or -O-(CH2) m -NH-C(=O)-, m is an integer of 2 or 4.] The chloride monomer (a2) is chloroethylene, The isocyanate derivative (B) is a compound obtained by reacting a hydrocarbon group alcohol having an alkyl group having 12 or more and 25 or less carbon atoms with an isocyanurate derivative of an acyclic aliphatic polyisocyanate having an aliphatic hydrocarbon group having 2 or more and 10 or less carbon atoms, or a compound obtained by reacting a sorbitol modifier modified with an alkyl group having 12 or more and 25 or less carbon atoms with a biuret derivative of an acyclic aliphatic polyisocyanate having an aliphatic hydrocarbon group having 2 or more and 10 or less carbon atoms, The amount of the isocyanate derivative (B) is 1 to 10 parts by weight relative to 100 parts by weight of the above-mentioned non-fluorinated copolymer (A).

[0019] [Item 13] A method for manufacturing a fiber article, comprising the step of applying the water-repellent composition described in any one of items 1 to 12 to a fiber substrate.

[0020] [Item 14] A method for manufacturing a fiber article as described in Item 13, comprising a step of imparting functional groups to the fiber before applying the water-repellent composition to the fiber substrate, wherein the functional groups are selected from -SO3M 1 (where M) 1 The monovalent group (representing a monovalent cation) is shown as -COOM. 2 (where M) 2 The monovalent group (representing a monovalent cation) and -O-P(O) (OX) are shown. 1 (OX) 2 (where X) 1 and X 2 One or more monovalent groups (each independently representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) are shown.

[0021] [Item 15] A fiber article having attached the above-mentioned non-fluorinated copolymer (A) and the above-mentioned isocyanate derivative (B) in any one of items 1 to 12 of the water-repellent composition.

[0022] [Item 16] The fiber article as described in Item 15, wherein an adhesive is attached with a material selected from SO3M 1 (where M) 1 The monovalent group (representing a monovalent cation) is shown as -COOM. 2 (where M) 2 The monovalent group (representing a monovalent cation) and -O-P(O) (OX) are shown. 1 (OX) 2 (where X) 1 and X 2 A compound that contains one or more functional groups, each representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and is indicated by a monovalent group.

[0023] Invention Effects The water-repellent composition of the present invention can impart both good water repellency and good slip resistance to the substrate (especially fibrous products). Detailed Implementation

[0024] <Definition of Terms> In this specification, "n-valent group" refers to a group having n valence bonds, that is, a group forming n bonds. Additionally, "n-valent organic group" refers to a carbon-containing n-valent group. There is no particular limitation on such organic groups; they can be hydrocarbon groups or their derivatives. Hydrocarbon derivatives refer to groups having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, or other groups at the end of the hydrocarbon group or in the molecular chain.

[0025] In the context of this specification, "hydrocarbon group" refers to a group containing carbon and hydrogen, specifically a group that has had a hydrogen atom removed from a hydrocarbon. There are no particular limitations on what constitutes such a hydrocarbon group; examples include C. 1－20 Hydrocarbon groups, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aforementioned "aliphatic hydrocarbon group" can be any of the following: straight-chain, branched-chain, or cyclic; and can be any of the following: saturated or unsaturated. Furthermore, the hydrocarbon group can also contain one or more ring structures, and the hydrocarbon group can be substituted by one or more substituents.

[0026] In this specification, whether or not the terms "independent each time it appears", "independent of each other", "independent of each other" or the same expression are explicitly stated, unless otherwise stated, when a term (symbol) that may appear multiple times is defined in a chemical structure, the definition shall be applied independently each time it appears.

[0027] It should be understood that the chemical structures described in this specification do not include chemical structures that are considered chemically impossible or extremely unstable by those skilled in the art.

[0028] <Water-repellent composition> The water-repellent composition of the present invention comprises a non-fluorinated copolymer (A) and an isocyanate derivative (B). The non-fluorinated copolymer (A) comprises repeating units derived from a hydrophobic monomer (a1) and repeating units derived from a chloride monomer (a2), wherein the monomer (a1) has a hydrocarbon group having 2 to 40 carbon atoms, and the monomer (a2) is at least one selected from vinyl chloride and vinylidene chloride. The water-repellent composition of the present invention can adhere to a substrate (particularly fibrous articles), thereby imparting both good water repellency and good slip resistance to the substrate.

[0029] The water-repellent composition may also contain other ingredients (organosilicon, wax, organic acid, surfactant, organic solvent, etc.).

[0030] [(A) Non-fluorinated copolymer] The non-fluorinated copolymer (A) does not contain fluorine atoms.

[0031] The nonfluorinated copolymer (A) comprises repeating units derived from a hydrophobic monomer (a1) and repeating units derived from a chloride monomer (a2). The nonfluorinated copolymer (A) may also comprise a monomer containing a cyclic hydrocarbon group (a3) ​​and / or a crosslinking monomer (a4). The nonfluorinated copolymer (A) may also comprise other monomers (a5).

[0032] (a1) Hydrophobic monomer) The hydrophobic monomer (a1) has an olefinic unsaturated double bond and a hydrocarbon group with 2 to 40 carbon atoms.

[0033] The hydrophobic monomer (a1) may have at least one hydrocarbon group having 2 to 40 carbon atoms. This hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The hydrocarbon group may be linear or branched, 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, preferably 6 or more. The number of carbon atoms in the hydrocarbon group may be 40 or less, 30 or less, 25 or less, 22 or less, or 20 or less, preferably 30 or less.

[0034] The hydrophobic monomer (a1) can be represented by the following formula: CH2=C(-R 12 ) - C (= O) - Y 11 - (R) 11 ) k The monomer shown.

[0035] [In the formula,] R 11 It consists of hydrocarbon groups with 2 to 40 carbon atoms. R 12 It can be a hydrogen atom, a monovalent organic group, or a halogen atom. Y 11 A 2- to 4-valent hydrocarbon group consisting of at least one of the following: -C6H4-, -O-, -C(=O)-, -S(=O)2-, and -NR'- (where R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). k is between 1 and 3. R 11The hydrocarbon group is preferably branched or straight-chain (preferably long-chain straight-chain) in shape. The hydrocarbon group is preferably aliphatic, particularly saturated aliphatic, and especially alkyl. The surface free energy of the -CH3 group is lower than that of the -CH2- group, making it more prone to liquid repellency. Therefore, structures with many branches and many -CH3 groups are preferred. On the other hand, long-chain alkyl groups of a certain length exhibit high liquid repellency due to their crystallinity. Therefore, it can be a branched hydrocarbon group (e.g., a branched alkyl group), particularly tert-butyl or isopropyl, a multi-branched group, or a long-chain hydrocarbon group (or a long-chain straight-chain hydrocarbon group), such as an alkyl group. 11 The number of carbon atoms can 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, preferably 10 or more. 11 The number of carbon atoms can be less than 40, less than 30, less than 25, less than 20, less than 15, or less than 12.

[0036] k is 1, 2, or 3. In Y 11 In the case of hydrocarbon groups with one carbon atom in the tetravalent state, k = 3. In Y... 11 In the case of hydrocarbon groups with one trivalent carbon atom, k = 2. In Y... 11 Cases without a hydrocarbon group having 1 carbon atom in either trivalent or tetravalent form (e.g., Y). 11 In the case of a hydrocarbon group (-CH2-) with 1 carbon atom in divalent form (e.g., 1 to 6), k = 1.

[0037] R 12 It can be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. R 12 Examples include hydrogen atoms, methyl groups, chlorine atoms, bromine atoms, iodine atoms, and cyano groups. R 12 Preferably, it contains hydrogen atoms, methyl groups, or chlorine atoms. R 12 More preferably, it is methyl. (Through R) 12 As a methyl group, it provides higher liquid-repellent properties. Especially from a reactivity point of view, R... 12 It can be a hydrogen atom.

[0038] Y 11 Preferably, the group is divalent. Examples of hydrocarbon groups with 1 carbon atom in the divalent to tetravalent range include -CH2-, -CH= with a branched structure, and -C≡ with a branched structure.

[0039] Y 11Can be -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'-.

[0040] [In the formula, Y' is independently a valence bond, -O-, -NR'- (R' is a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms) or -S(=O)2-, X' is -(CH2) m - (m is an integer from 1 to 5), a straight-chain hydrocarbon group with 1 to 5 carbon atoms and unsaturated bonds, a hydrocarbon group with 1 to 5 carbon atoms and a branched structure, or - (CH2). l -C6H4-(CH2) l — (l represents an independent integer from 0 to 5, and -C6H4- represents phenylene). Preferred Y 11 Not all of them are divalent hydrocarbon groups.

[0041] Y 11 Specific examples include -O-, -NH-, -O-C(=O)-, -NH-C(=O)-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -NH-C6H4-, and -O-(CH2). m -O-, -NH- (CH2) m -NH-, -O- (CH2) m -NH-, -NH-(CH2) m -O-, -O- (CH2) m -O-C (=O)-, -O- (CH2) m -C (=O) -O-, -NH- (CH2) m -O-C (=O)-, -NH- (CH2) m -C (=O) -O-, -O- (CH2) m -O-C (=O)-NH-, -O- (CH2) m -NH-C (=O) -O-, -O- (CH2) m -C (=O) -NH-, -O- (CH2) m -NH-C (=O)-, -O- (CH2) m -NH-C (=O) -NH-, -O- (CH2) m -O-C6H4-, -O- (CH2) m-NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2-, -NH-(CH2) m -S(=O)2-NH--NH-(CH2) m -O-C (=O)-NH-, -NH- (CH2) m -NH-C (=O) -O-, -NH- (CH2) m -C (=O) -NH-, -NH- (CH2) m -NH-C (=O)-, -NH- (CH2) m -NH-C (=O) -NH-, -NH- (CH2) m -O-C6H4- or -NH-(CH2) m -NH-C6H4- [where m is an integer from 1 to 5, especially 2 or 4].

[0042] Y 11 Preferably, it is -O-, -NH-, or -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, especially 2 or 4].

[0043] Y 11 More preferably, -O- or -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-, especially -O-(CH2) m -NH-C(=O)-.

[0044] Y 11 Further preferred are -O- and -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, especially 2 or 4].

[0045] Y 11 Particularly preferred are -O- or -O-(CH2)2-NH-C(=O)-.

[0046] The preferred hydrophobic monomer (a1) does not possess either reactive or hydrophilic groups. Examples of reactive groups include epoxy, chloromethyl, bromomethyl, iodomethyl, isocyanate, and terminal isocyanate groups. Examples of hydrophilic groups include hydroxyl, polyoxyalkylene, amino, carboxylic acid, sulfonic acid, phosphoric acid, alkali metal or alkaline earth metal salts of carboxylic acid, sulfonic acid, and phosphoric acid, ammonium salts with chlorine, bromine, or iodide ions as balanced anions, and other ionic groups. Reactive and hydrophilic groups can be repeated.

[0047] The water solubility of the hydrophobic monomer (a1) at 25°C can be less than 10 g / L, less than 5 g / L, less than 3 g / L, less than 1 g / L, less than 0.5 g / L, or less than 0.1 g / L, preferably less than 3 g / L. The water solubility of the homopolymer of the hydrophobic monomer (a1) at 25°C can be less than 10 g / L, less than 5 g / L, less than 3 g / L, less than 1 g / L, less than 0.5 g / L, or less than 0.1 g / L, preferably less than 3 g / L.

[0048] The water contact angle of the homopolymer of the hydrophobic monomer (a1) can be 75° or more, 80° or more, 85° or more, 90° or more, 95° or more, 100° or more, 101° or more, 103° or more, 105° or more, 110° or more, 115° or more, or 120° or more, preferably 90° or more or 100° or more. The water contact angle of the homopolymer of the hydrophobic monomer (a1) can be 160° or less, 150° or less, 140° or less, 130° or less, 125° or less, or 110° or less. From the viewpoint of the liquid repellency, especially the water repellency, of the copolymer, the water contact angle within the above range is preferred. The water contact angle of the homopolymer is obtained by spin-coating a 1.0% chloroform solution of the solid component of the homopolymer onto a silicon wafer substrate, adding 2 μL of water to the coating, and measuring the contact angle after 1 second.

[0049] Specific examples of hydrophobic monomers (a1) are as follows. The compounds with the following chemical formulas are acrylic acid compounds with a hydrogen atom at the α-position, but they can also be methacrylic acid compounds with a methyl atom at the α-position and α-chloroacrylic acid compounds with a chlorine atom at the α-position.

[0050] 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 CH2=CHC(=O)OC m H 2m NHSO2C n H 2n＋1 CH2=CHC(=O)OC m H 2m SO2NHC n H 2n＋1 [In the above formula, n is a number from 3 to 40, and m is a number from 1 to 5.] Preferred specific examples of hydrophobic monomers (a1) include stearyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, eicosyl (meth)acrylate, bezoaryl (meth)acrylate, stearyl α-chloroacrylate, eicosyl α-chloroacrylate, bezoaryl α-chloroacrylate, stearamide ethyl (meth)acrylate, 2-stearamide ethyl acrylate, CH2=CHC(=O)OC2H4NHSO2C 18 H 37 They can be used individually or in combination.

[0051] From the viewpoint of the dispersibility of the dispersion, the hydrophobic monomer (a1) can comprise a hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group. It can also be a combination of a hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group and a hydrophobic monomer (a1) not having an amide group, a urea group, or a urethane group. As an example of a hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group, CH2=C(-R) can be cited. 12 )-C(=O)-O-(CH2) m -NH-C(=O)-R 11 CH2=C(-R 12 )-C(=O)-O-(CH2) m -O-C (=O)-NH-R 11 CH2=C(-R 12)-C(=O)-O-(CH2) m -NH-C(=O)-O-R 11 and CH2=C(-R) 12 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R 11 Etc. Hydrophobic monomers (a1) may also contain CH2=C(-R). 12 )-C(=O)-O-(CH2) m -NH-C(=O)-R 11 .

[0052] ((a2) chloride monomer) The non-fluorinated copolymer (A) comprises repeating units derived from at least one chloride monomer (a2) selected from vinyl chloride and vinylidene chloride. The chloride monomer (a2) is preferably vinyl chloride.

[0053] ((a3) Monomers containing cyclic hydrocarbon groups) The non-fluorinated copolymer (A) may have repeating units derived from a monomer (a3) ​​containing a cyclic hydrocarbon group. The monomer (a3) ​​containing a cyclic hydrocarbon group is a monomer having a cyclic hydrocarbon group, which may be a monomer having an olefinic unsaturated double bond and a cyclic hydrocarbon group.

[0054] The monomer (a3) ​​containing a cyclic hydrocarbon group preferably has a (meth)acrylate group as an olefinic unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as an olefinic unsaturated double bond.

[0055] The cyclic hydrocarbon group can be aliphatic or aromatic, preferably aliphatic. The cyclic hydrocarbon group can be saturated or unsaturated, preferably saturated. The cyclic hydrocarbon group can be monocyclic, polycyclic, or bridged, preferably bridged. The cyclic hydrocarbon group can also have chain-like groups (e.g., straight-chain or branched hydrocarbon groups).

[0056] The number of carbon atoms in a cyclic hydrocarbon group can be 4 or more, 6 or more, or 8 or more, and can be less than 30, 26 or less, 22 or less, 18 or less, or 14 or less.

[0057] Specific examples of cyclic hydrocarbon groups include cyclohexyl, tert-butylcyclohexyl, adamantyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, borneol, isoborneol, norbornenyl, dicyclopentyl, dicyclopentenyl, benzyl, phenyl, naphthyl, 2-tert-butylphenyl, residues from which one or more hydrogen atoms have been removed (e.g., cyclohexene, adamantyl, phenylene, naphthylene, etc.), and groups that are substitutes for them.

[0058] Specific examples of monomers containing cyclic hydrocarbon groups (a3) ​​include cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentoxyethyl (meth)acrylate, tricyclopentyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and compounds in which these acrylates are replaced with acrylamides. They can be used alone or in combination of two or more.

[0059] (a4) cross-linking monomers) The non-fluorinated copolymer (A) may also have repeating units derived from the crosslinking monomer (a4). The crosslinking monomer (a4) is a monomer capable of imparting crosslinking properties to the copolymer and may have at least two selected from reactive groups and olefinic carbon-carbon double bonds. The crosslinking monomer (a4) may be a compound having at least two olefinic unsaturated double bonds, or a compound having at least one olefinic unsaturated double bond and at least one reactive group.

[0060] The crosslinking monomer (a4) preferably has a (meth)acrylate group as an olefinic unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as an olefinic unsaturated double bond.

[0061] Examples of reactive groups include hydroxyl, epoxy, chloromethyl, terminal isocyanate group, amino, carboxyl, carbonyl, and isocyanate group (terminated isocyanate group).

[0062] Specific examples of crosslinking monomers (a4) include diacetone (meth)acrylamide, N-hydroxymethyl (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-acetylacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and compounds in which these acrylates are replaced with acrylamides. They can be used alone or in combination of two or more.

[0063] ((a5) other monomers) The non-fluorinated copolymer (A) may also contain repeating units derived from other monomers (a5) besides monomers (a1) to (a4).

[0064] Specific examples of other monomers (a5) include ethylene, haloolefins, vinyl acetate, acrylonitrile, alkoxy polyalkylene glycol (meth)acrylates, and vinyl alkyl ethers. Other nonfluorinated monomers are not limited to these examples. They can be used alone or in combination of two or more.

[0065] (Polymer composition) The amount of repeating units derived from the hydrophobic monomer (a1) relative to the non-fluorinated copolymer (A) can be 50% or more by weight, 60% or more by weight, 65% or more by weight, 70% or more by weight, 75% or more by weight, 80% or more by weight, or 85% or more by weight. The amount of repeating units derived from the hydrophobic monomer (a1) relative to the non-fluorinated copolymer (A) can be 99% or less by weight, 98% or less by weight, 95% or less by weight, 90% or less by weight, 80% or less by weight, 70% or less by weight, or 60% or less by weight.

[0066] In the repeating unit derived from the hydrophobic monomer (a1), the proportion of the hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group can be 1% or more by weight, 3% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, 50% or more by weight, or 75% or more by weight. In the repeating unit derived from the hydrophobic monomer (a1), the proportion of the hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group can be 100% or less by weight, 90% or less by weight, 80% or less by weight, or 70% or less by weight.

[0067] The amount of repeating units derived from the chloride monomer (a2) relative to the non-fluorinated copolymer (A) can be 1% or more by weight, 2% or more by weight, 3% or more by weight, 4% or more by weight, or 5% or more by weight. The amount of repeating units derived from the chloride monomer (a2) relative to the non-fluorinated copolymer (A) can be 15% or less by weight, 13% or less by weight, 11% or less by weight, 10% or less by weight, 9% or less by weight, 8% or less by weight, 7% or less by weight, 6% or less by weight, or 5% or less by weight.

[0068] In the non-fluorinated copolymer (A), the amount of repeating units derived from chloride monomer (a2) can be 1% or more by weight, 2% or more by weight, 3% or more by weight, 4% or more by weight, or 5% or more by weight, with a preference of 3% or more by weight, relative to the total amount of repeating units derived from hydrophobic monomer (a1) and repeating units derived from chloride monomer (a2).

[0069] In the non-fluorinated copolymer (A), the amount of repeating units derived from chloride monomer (a2) can 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, preferably 10% by weight or less, and more preferably 7% by weight or less, relative to the total amount of repeating units derived from hydrophobic monomer (a1) and repeating units derived from chloride monomer (a2).

[0070] The amount of repeating units derived from the monomer (a3) ​​containing cyclic hydrocarbon groups relative to the non-fluorinated copolymer (A) can be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more. The amount of repeating units derived from the monomer (a3) ​​containing cyclic hydrocarbon groups relative to the non-fluorinated copolymer (A) can 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.

[0071] The amount of repeating units derived from the crosslinking monomer (a4) relative to the non-fluorinated copolymer (A) can be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more. The amount of repeating units derived from the crosslinking monomer (a4) relative to the non-fluorinated copolymer (A) can 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.

[0072] The amount of repeating units derived from other monomers (a5) relative to the non-fluorinated copolymer (A) can be 0.5% or more by weight, 1% or more by weight, 3% or more by weight, or 4% or more by weight. The amount of repeating units derived from other monomers (a5) relative to the non-fluorinated copolymer (A) can be less than 30% by weight, less than 20% by weight, less than 15% by weight, less than 10% by weight, or less than 5% by weight.

[0073] The amount of repeating units derived from chloride monomer (a2) may be 1 part or more, 3 parts or more, 5 parts or more, 10 parts or more, 25 parts or more, 50 parts or more, 75 parts or more, or 100 parts or more, relative to 100 parts by weight of repeating units derived from hydrophobic monomer (a1). The amount of repeating units derived from chloride monomer (a2) may be less than 150 parts by weight, less than 125 parts by weight, less than 100 parts by weight, less than 75 parts by weight, less than 50 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, less than 8 parts by weight, less than 7 parts by weight, or less than 6 parts by weight, relative to 100 parts by weight of repeating units derived from hydrophobic monomer (a1).

[0074] The amount of repeating units derived from the monomer containing a cyclic hydrocarbon group (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, relative to 100 parts by weight of repeating units derived from the hydrophobic monomer (a1). The amount of repeating units derived from the monomer containing a cyclic hydrocarbon group (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, relative to 100 parts by weight of repeating units derived from the hydrophobic monomer (a1).

[0075] The amount of repeating units derived from the crosslinking 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, relative to 100 parts by weight of repeating units derived from the hydrophobic monomer (a1). The amount of repeating units derived from the crosslinking 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, relative to 100 parts by weight of repeating units derived from the hydrophobic monomer (a1).

[0076] 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, relative to 100 parts by weight of repeating units derived from hydrophobic monomers (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, relative to 100 parts by weight of repeating units derived from hydrophobic monomers (a1).

[0077] [(B) Isocyanate derivatives] Isocyanate derivatives (B) are compounds obtained by reacting active hydrogen compounds with raw isocyanates. They have a portion derived from compounds containing active hydrogen and a portion derived from the raw isocyanate. Unlike isocyanate-based curing agents, isocyanate derivatives (B) typically do not contain isocyanate groups.

[0078] The isocyanate derivative (B) has a -NHCO- group formed by the reaction of an active hydrogen compound with the starting isocyanate (wherein the -NHCO- group can be part of a urethane or urea group). The -NHCO- group is formed by the reaction of the active hydrogen-containing group (typically a hydroxyl group) of compound (a) with the active hydrogen reactive group (typically an isocyanate group) of compound (b). The isocyanate derivative (B) is typically a urethane (especially a polyurethane).

[0079] 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, preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group (alkyl). The hydrocarbon group may be branched, cyclic, or linear, more preferably chain-like, especially 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, 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, preferably 30 or less, 25 or less, or 20 or less.

[0080] 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, particularly linear. The alkyl group in 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, preferably 12 or more or 16 or more. The alkyl group in the isocyanate derivative (B) may have 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0081] The weight-average molecular weight of isocyanate derivative (B) can be above 3000, above 5000, above 10000, above 30000, above 100000, above 300000, or above 500000. The weight-average molecular weight of isocyanate derivative (B) can be below 1000000, below 750000, below 500000, below 300000, below 100000, below 75000, below 50000, below 30000, below 10000, or below 5000.

[0082] The water contact angle of the isocyanate derivative (B) can 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) can be less than 160°, less than 140°, less than 130°, less than 120°, less than 110°, less than 100°, or less than 90°. By having a water contact angle of the lower limit or higher than the above-mentioned values, the isocyanate derivative (B) can impart good water repellency to the substrate. The water contact angle is the static contact angle of the isocyanate derivative (B) with respect to the spin-coated film, obtained by adding 2 μL of water to the spin-coated film and measuring the contact angle after 1 second.

[0083] [Active hydrogen compounds] Active hydrogen compounds contain active hydrogen groups that react with isocyanate groups.

[0084] Examples of active hydrogen groups include hydroxyl, amino, and carboxyl groups, with hydroxyl being a typical example.

[0085] [(α1) Hydroxyl alcohol] Active hydrogen compounds can be hydrocarbon alcohols (α1) composed of hydrocarbon groups and hydroxyl groups.

[0086] The hydrocarbon group in the alkyl alcohol (α1) can be a hydrocarbon group with 6 to 40 carbon atoms as described above, and the above description continues. The hydrocarbon group in the alkyl alcohol (α1) is preferably an alkyl group with 12 to 30 carbon atoms as described above, and the above description continues.

[0087] Furthermore, the hydrocarbon alcohol (α1) preferably has one hydroxyl group per molecule.

[0088] Examples of alkyl alcohols (α1) include: alcohols containing straight-chain saturated hydrocarbon groups such as n-tetranol, n-tetradecanool, n-pentadecanool, n-hexadecanool, n-heptadecanool, n-octadecanool (stearyl), n-nonadecanol, and eicosanool; alcohols containing branched saturated hydrocarbon groups such as isomyristol, isocetyl alcohol, isostearyl alcohol, and isoeicosanool; alcohols containing straight-chain unsaturated hydrocarbon groups such as tetradecenol, hexadecenol, oleyl alcohol, eicosenoenol, dodecenol, dodecenol, dodecenol, dodecenol, dodecenol, dodecenol, and dodecenol; and active hydrogen compounds containing branched unsaturated hydrocarbon groups such as phytol.

[0089] Here, alcohols containing straight-chain saturated hydrocarbon groups and alcohols containing straight-chain unsaturated hydrocarbon groups can be used together. When alcohols containing straight-chain saturated hydrocarbon groups and alcohols containing straight-chain unsaturated hydrocarbon groups are used together, the proportion of alcohols containing straight-chain saturated hydrocarbon groups is, for example, 40 parts by weight or more, preferably 55 parts by weight or more, more preferably 70 parts by weight or more, and for example, 90 parts by weight or less, preferably 80 parts by weight or less, relative to the total amount of alcohols containing straight-chain saturated hydrocarbon groups and alcohols containing straight-chain unsaturated hydrocarbon groups, is, for example, 10 parts by weight or more, preferably 20 parts by weight or more, and for example, 60 parts by weight or less, preferably 45 parts by weight or less, more preferably 30 parts by weight or less, relative to the total amount of alcohols containing straight-chain saturated hydrocarbon groups and alcohols containing straight-chain unsaturated hydrocarbon groups. When the proportion of alcohols containing straight-chain saturated hydrocarbon groups is above the lower limit mentioned above, the crystallinity of the hydrocarbon groups is improved, resulting in enhanced water repellency of the water-repellent product treated with the water-repellent composition.

[0090] [(α2) Sugar alcohol / hydroxy acid modified form] Active hydrogen compounds can be sugar alcohol / hydroxy acid modifiers (α2), which are sugar alcohols / hydroxy acids (sugar alcohols and / or hydroxy acids) modified with hydrocarbon groups having 6 to 40 carbon atoms. The types of sugar alcohols / hydroxy acids are not limited and can be cyclic or acyclic. Examples of sugar alcohols include monosaccharides, reducing sugars, amino sugars, aldonic acids, and aldonic acid lactones. Examples of hydroxy acids include hydroxy polycarboxylic acids. Sugar alcohols / hydroxy acids can be substances present in living organisms. Examples of sugar alcohols / hydroxy acids include compounds derived from aldoses and ketoses, such as compounds derived from teuoses, pentoses, hexoses, and heptoses, but are not limited to these. Specific examples include: glucose, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, azoose, mannose, xylose, lysose, gulose, galactose, tarose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol, threitol, glucopyranose, mannoheptulose, taropeptulose, pyranoalose, pyranoalose, pyranoalose, pyranoidulose, pyranogulose, glucitol, mannitol, erythritol, sorbitol, arabinitol, xylitol, ribitol, galactitol, fucitol, idulitol, inositol, pentaerythritol, dipentaerythritol, heptaheptanol, gluconic acid, glyceric acid, xylic acid, galactopyric acid, ascorbic acid, citric acid, gluconolactone, glycerolactone, xylonolactone, glucosamine, galactosamine, or mixtures thereof. The sugar alcohol / hydroxy acid may have 2 or more, 4 or more, or 6 or more carbon atoms, and may have 30 or less, 20 or less, or 10 or less. The average OH value of the compound (α2) may be greater than 0 and less than about 230, preferably from about 10 to about 175, and most preferably from about 25 to about 140.

[0091] The number of hydrocarbon groups with 6 to 40 carbon atoms in the sugar alcohol / hydroxy acid modified body (α2) can be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more. The number of hydrocarbon groups with 6 to 40 carbon atoms in the sugar alcohol / hydroxy acid modified body (α2) can be 12 or less, 9 or less, 6 or less, or 3 or less. The hydrocarbon groups in the sugar alcohol / hydroxy acid modified body (α2) can be the hydrocarbon groups with 6 to 40 carbon atoms as described above, following the explanation above. The sugar alcohol / hydroxy acid modified body (α2) can have alkyl groups with 12 to 30 carbon atoms. Regarding alkyl groups with 12 to 30 carbon atoms, following the explanation above.

[0092] In the sugar alcohol / hydroxy acid modified (α2), at least one active hydrogen atom (e.g., the hydrogen atom of the OH group or the carboxyl group) of the sugar alcohol and / or hydroxy acid can be selected from -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, the active hydrogen substituents of mixtures thereof. Here, R α2 The hydrocarbon group having 6 to 40 carbon atoms is a hydrogen atom or a hydrocarbon group having 0 to 20 carbon atoms, each n is independently 0 to 20, each m is independently 0 to 20, and m + n can be greater than 0. The compound (α2) has at least one active hydrogen atom. For example, in the sugar alcohol / hydroxy acid modified body, at least one (one or more) active hydrogen atom of the sugar alcohol / hydroxy acid may be unmodified. This active hydrogen atom (e.g., -OH group) may also react with the active hydrogen reactive group (especially the isocyanate group) of the compound (b) to form -NHCO-. The hydrocarbon group having 6 to 40 carbon atoms in the sugar alcohol / hydroxy acid modified body (α2) is preferably an alkyl group having 12 to 30 carbon atoms as described above, following the above description.

[0093] ((α21) dehydrated sorbitol modified form) The sugar alcohol / hydroxy acid modifier (α2) can be the dehydrated sorbitol modifier (α21) after modifying dehydrated sorbitol with a hydrocarbon group having 6 to 40 carbon atoms, and in particular it can be an alkyl dehydrated sorbitol, or it can be a dehydrated sorbitol modified with -R α2 -C(O)R α2 - (CH2CH2O) n (CH(CH3)CH2O) m R α2 - (CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 Or mixtures thereof replacing compounds of sorbitol (here R) α2 (A hydrocarbon group with 6 or more carbon atoms). For example, it can be a hydrocarbon group using -C(O)R α2 Compounds obtained by mono-, di-, or tri-substituted dehydrated sorbitol. The dehydrated sorbitol may contain a certain amount of sorbitol, isosorbide, or other intermediates or byproducts. The hydrocarbon group in the dehydrated sorbitol modified body (α21) may be a hydrocarbon group with 6 to 40 carbon atoms, as described above. The dehydrated sorbitol modified body (α21) may have an alkyl group with 12 to 30 carbon atoms. Regarding alkyl groups with 12 to 30 carbon atoms, as described above. Commercially available dehydrated sorbitols such as SPAN can be used as the aforementioned alkyl dehydrated sorbitols.

[0094] In one manner, at least one active hydrogen substituent can be -C(O)R α2 R α2The alkyl group may be a straight-chain or branched alkyl group with 6 to 40 carbon atoms, more preferably 7 to 21, and most preferably 11 to 21. Preferred compounds include mono-, di-, and tri-substituted sorbitol esters derived from octanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, sorbic acid, lignoceric acid, and mixtures thereof. Particularly preferred compounds include mono-, di-, and tri-substituted sorbitol stearate or sorbitol sorbitol sorbate. Particularly preferred compounds include mono-, di-, and tri-substituted sorbitol stearate or sorbitol sorbate.

[0095] In one approach, R α2 It may contain at least one unsaturated bond. An example of such a compound is one in which at least one active hydrogen substituent is selected from -C(O)R. α2 R α2 Having at least one unsaturated bond, an example is trioleic acid dehydrated sorbitol ester (i.e., R in the formula). α2 -C7H 14 CH=CHC8H 17 (but not limited to these). Other examples include mono-substituted, di-substituted, and tri-substituted dehydrated sorbitol esters derived from palmitoleic acid, linoleic acid, arachidonic acid, and erucic acid, but are not limited to these.

[0096] In one embodiment, the sorbitol-modified form (α21) has at least one active hydrogen substituent, which may independently be -(CH2CH2O). n (CH(CH3)CH2O) m R α2 Or - (CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 Each m independently ranges from 0 to 20, each n independently ranges from 0 to 20, and m + n is greater than 0. Such compounds are well-known as polysorbates and are marketed under the trademark TWEEN. They can utilize R... α2 These dehydrated sorbitols are subjected to mono-, di-, or tri-substituted substitutions. Commercially available polysorbates are known to contain substances derived from various R... 2 Various polysorbates of H (unsubstituted) to various R α2 This refers to a mixture of various substances containing straight-chain or branched alkyl groups having 6 to 40 carbon atoms (fully substituted), and mixtures of various substituted derivatives of these substances. Examples of such dehydrated sorbitol modifiers (α21) include polysorbates such as polysorbate tristearate and polysorbate monostearate. As for m+n greater than 0 and R... α2Examples of dehydrated sorbitol modifiers (α21) containing at least one unsaturated bond are not limited, but can be listed as polysorbate trioleate (where R α2 C7H 14 CH=CHC8H 17 It is marketed as polysorbate 80. The dehydrated sorbitol modifier (α21) can contain a mixture of compounds with various active hydrogen substituents, or it can contain R... α2 Compounds containing at least one unsaturated bond and R α2 A mixture of fully saturated compounds.

[0097] ((α22)citric acid modified form) The sugar alcohol / hydroxy acid modifier (α2) can be a citric acid modifier (α22) modified with a hydrocarbon group having 6 to 40 carbon atoms, particularly an alkyl ester of citrate. For example, the citric acid modifier (α22) can exist as a monosubstituted, disubstituted, or trisubstituted form having an alkyl group. The hydrocarbon group in the citric acid modifier (α22) can be one of the hydrocarbon groups having 6 to 40 carbon atoms as described above, following the description above. The citric acid modifier (α22) can have an alkyl group having 12 to 30 carbon atoms. For alkyl groups having 12 to 30 carbon atoms, following the description above. A mixture of citrate esters with various values ​​of active hydrogen substituents can be used, and it can also contain R... α2 Compounds with at least one unsaturated hydrocarbon group and R α2 This is a mixture of compounds that are fully saturated hydrocarbons. The citric acid-modified form (α22) can have a composition selected from -(CH2CH2O). n (CH(CH3)CH2O) m R α2 Or - (CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 The active hydrogen substituent (in this case R) α2 (A hydrocarbon group with 6 to 40 carbon atoms). Examples of citric acid modifiers (α22) include trialkyl citrates, but are not limited to these.

[0098] ((α23) pentaerythritol modified form) The sugar alcohol / hydroxy acid modifier (α21) can be a pentaerythritol modifier (α23) modified with a hydrocarbon group having 6 to 40 carbon atoms, and can be a monosubstituted, disubstituted, or trisubstituted derivative having a hydrocarbon group (especially an alkyl group) having 6 to 40 carbon atoms, such as a dipentaerythritol ester. α2 ]3 (where Rα2 (A hydrocarbon group with 6 to 40 carbon atoms). Furthermore, the pentaerythritol modifier (α23) can contain compounds of varying chain lengths with hydrocarbon groups or R. α2 Compounds containing at least one unsaturated bond, and R α2 A mixture of fully saturated compounds. The hydrocarbon group in the pentaerythritol modifier (α23) can be a hydrocarbon group with 6 to 40 carbon atoms as described above, following the explanation above. The pentaerythritol modifier (α23) can have an alkyl group with 12 to 30 carbon atoms. Regarding alkyl groups with 12 to 30 carbon atoms, following the explanation above.

[0099] [(α3) cationic active hydrogen compounds] Active hydrogen compounds can be cationic active hydrogen compounds (α3) that have active hydrogen groups and cationic groups.

[0100] Furthermore, the cationic active hydrogen compound (α3) preferably has two or more hydroxyl groups per molecule.

[0101] Examples of cationic groups include tertiary amino groups.

[0102] That is, the cationic active hydrogen compound (α3) preferably has two or more hydroxyl groups per molecule as active hydrogen groups and tertiary amino groups as cationic groups.

[0103] Based on such cationic active hydrogen compounds, good dispersibility in liquid media (e.g., water) can be imparted, and cationic groups with affinity for fibrous products (described later) can be introduced into the resin, thus improving wash durability.

[0104] 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.

[0105] Examples of such cationic active hydrogen compounds include alkyl dialkyl alcoholamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, and propanolamine, or trialkyl alcoholamines such as N-triethanolamine and N-triisopropanolamine, with N-methyldiethanolamine being a preferred example.

[0106] Cationic active hydrogen compounds (or the portion of non-fluorinated copolymers derived from cationic active hydrogen compounds) can form salts with acid compounds.

[0107] 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. Organic acids are preferred as acid compounds. If the acid compound contains an organic acid, the water-repellent properties of the water-repellent product treated with this water-repellent composition can be improved by evaporating the acid through heat treatment. Furthermore, from the viewpoint that cationic groups readily adsorb onto fiber products, the wash durability of the fiber products can be improved by evaporating the acid through heat treatment.

[0108] [(α4) Other compounds containing active hydrogen] Active hydrogen compounds (α) may contain other compounds containing active hydrogen (α4).

[0109] ((α41) compound) Active hydrogen compounds (α4) can be of formula R α41 -X α41 The compound shown is (α41).

[0110] [In the formula,] R α41 For C1 to C2 groups that can contain at least one unsaturated group 30 Straight-chain or branched alkyl, hydroxyl functionalities C1-C 30 Straight-chain or branched alkyl, hydroxyl functional straight-chain or branched C1-C 30 Polyethers, hydroxyl-functional linear or branched polyesters, hydroxyl-functional linear or branched organosiloxanes, and thiol-functional C1-C64 polymers. 30 Straight-chain or branched alkyl, amine functionality C1-C 30 Straight-chain or branched alkyl groups, Y － R α411 R α412 R α413 N ＋ -R α414 - (where Y is a halide ion, such as Cl) － HOS (=O)2-R α414 - or R α411 R α412 C = N - (where R) α411 R α412 R α413 Each is independently -H, C1 to C6 alkyl, R α414 (A divalent alkyl group having 1 to 20 carbon atoms). X α41 The possible values ​​are -OH, -C(O)OH, -SH, -NH(R'), and -O-(CH2CH2O). s(CH(CH3)CH2O) t -H or -C(O)-O-(CH2CH2O) s (CH(CH3)CH2O) t Isocyanate reactive functional groups such as -H (where R' is -H or a monovalent organic group, s is an integer from 0 to 50, t is an integer from 0 to 50, and s + t is greater than 0). Compound (α41) can be a hydrophilic, water-soluble material containing at least one hydroxyl-terminated polyether, where X α41 It is -O-(CH2CH2O). s (CH(CH3)CH2O) t -H or -C(O)-O-(CH2CH2O)s(CH(CH3)CH2O) t -H. -(CH2CH2O)- represents oxyethylidene (EO), -(CH(CH3)CH2O)- represents oxypropylene (PO). These polyethers may contain only EO groups, only PO groups, or mixtures thereof. Furthermore, these polyethers may exist in the form of a specified PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol) triblock copolymer.

[0111] In one manner, X α41 For -OH, -C(O)OH, -SH, -NH(R'), R α41 Arbitrarily selected from C1 to C1-C1 containing at least one unsaturated group. 30 Straight-chain or branched alkyl, hydroxyl functionalities C1-C 30 Straight-chain or branched alkyl, hydroxyl functional straight-chain or branched C1-C 30 Polyethers, hydroxyl-functional linear or branched polyesters, hydroxyl or amine-functional linear or branched organosiloxanes, and thiols-functional C1-C64... 30 Straight-chain or branched alkyl, amine functionality C1-C 30 Straight-chain or branched alkyl groups.

[0112] X α41 It can be -OH. Examples of such compounds (α41) include alkyl alcohols such as propanol and butanol, or aliphatic alcohols including stearyl alcohol (R... α41 Optionally, it is a C1-C1 group containing at least one unsaturated group. 30 (Straight-chain or branched alkyl); alkyl diols or polyols such as ethylene glycol, propylene glycol, butanediol or hexanediol (R α41 Hydroxyl functional C1~C 30(Straight-chain or branched alkyl); alkylene glycol ethers of triethylene glycol, tetraethylene glycol, polyethylene glycol (PEG), polypropylene glycol (PPG), polytetrahydrofuran, etc., or glycol ethers of mixtures having PEG, PPG, or THF units (R α41 It is a hydroxyl-functional straight-chain or branched C1-C1 chain. 30 Polyether); Polyester polyol (R) α41 (Hydroxy-functional linear or branched polyester); organosilicon prepolymer polyol (R) α41 (A hydroxyl-functional linear or branched organosiloxane); N,N-dimethylaminoethanol (R α41 Amine functional C1~C 30 Straight-chain or branched alkyl groups); choline chloride or betaine HCl (R α41 For Y － R α411 R α412 R α413 N ＋ -R α414 -), Butyl ketone oxime (R α41 For R α411 R α412 (C=N-), but not limited to these. Polyether polyols may contain only EO groups, only PO groups, only THF groups, or mixtures thereof. Furthermore, these polyethers may exist in the form of block copolymers of polymers such as PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). The polyether diol preferably has an average molecular weight of about 200 or more, most preferably 350 to 2000.

[0113] X α41 It can be -C(O)OH. Examples of such compounds (α41) include fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, benzyl acid, ceramide, palmitoleic acid, linoleic acid, arachidonic acid, oleic acid, or erucic acid (R). α41 Optionally, it is a C1-C1 group containing at least one unsaturated group. 30 Hydroxy acids (R-containing acids such as straight-chain or branched alkyl groups), hydroxyoctanoic acid, hydroxydecanoic acid, hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyarachidic acid, hydroxybeanic acid, hydroxywood wax acid, hydroxypalmitoic acid, hydroxylinoleic acid, hydroxyarachidonic acid, hydroxyoleic acid, or hydroxyerucic acid, etc. α41 Hydroxyl functional C1~C 30 Mercaptoalkyl acids (R) such as straight-chain or branched alkyl groups and mercaptopropionic acid α41 It is a thiol functional C1~C 30 (straight-chain or branched alkyl groups), but not limited to these.

[0114] X α41It can be -SH; examples of such compounds (α41) include alkyl thiols such as lauryl thiols or dodecyl thiols (R... α41 Optionally, it is a C1-C1 group containing at least one unsaturated group. 30 (straight-chain or branched alkyl groups), but not limited to these.

[0115] X α41 It can be -NH (R'), and examples of such compounds (α41) include alkylamines (R') such as diisopropylamine, propylamine, hexylamine, or laurylamine. α41 Optionally, it is a C1-C1 group containing at least one unsaturated group. 30 Alkylamines (R) such as straight-chain or branched alkyl groups, ethanolamines, or propanolamines α41 Hydroxyl functional C1~C 30 Straight-chain or branched alkyl groups), organosilicon prepolymer polyamines (R α41 (Amine-functional linear or branched organosiloxanes), alkyl diamines (R...) α41 Amine functional C1~C 30 Aminoalkylsulfonic acids (R) such as straight-chain or branched alkyl groups and 2-aminoethanesulfonic acid α41 is HO-S(O)2R α414 —), but not limited to these.

[0116] ((α42) compound) Compound (α42) is of formula R α421 - (OCH2CH(OR) α422 CH2) z -OR α423 .

[0117] [In the formula,] R α421 R α422 and R α423 In, at least one R α421 R α422 Or R α423 For -H, independently for -H and -R respectively. α424 -C(O)R α424 R α424 Independently, it is a straight-chain or branched alkyl group having 5 to 29 carbon atoms, which may contain at least one unsaturated bond, and z is 1 to 15. The compound (α42) can be a compound commonly referred to as polyglycerol. Other specific examples include, but are not limited to, triglyceride monostearate, triglyceride distearate, hexaglyceride monostearate, hexaglyceride distearate, decaglyceride mono(caprylate / capric acid ester), decaglyceride di(caprylate / capric acid ester), decaglycerol, polyglycerol-3 and C18 diglyceride.

[0118] (α43) chain extender) Compound (α4) can be a chain extender (α43). A chain extender (α43) is a compound having two or more (e.g., two) functional groups containing active hydrogen atoms within its molecule. As chain extenders, known chain extenders can be used, such as: aliphatic or aromatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanediethanolamine; aliphatic or aromatic diamines or polyamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, and diethyltoluenediamine; compounds containing phenolic hydroxyl groups 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 alcoholamines such as aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine, aminopropylpropanolamine, and aminohexylpropanolamine.

[0119] In one embodiment, the active hydrogen compound may be at least one selected from hydrocarbon alcohols, sugar alcohols, and hydroxy acid modifiers.

[0120] [Raw material isocyanate] Isocyanate derivative (B) has a portion derived from the raw material isocyanate.

[0121] The raw material isocyanate can be aromatic polyisocyanate, noncyclic aliphatic polyisocyanate, cyclic alicyclic polyisocyanate or bridged cyclic alicyclic polyisocyanate.

[0122] Aromatic polyisocyanates are compounds containing aromatic rings and isocyanate groups. The aromatic rings in aromatic polyisocyanates can be one or more, two or more, or three or more, and can be five or fewer, four or fewer, or three or fewer.

[0123] Acyclic aliphatic polyisocyanates are aliphatic polyisocyanates without a ring structure. Acyclic aliphatic polyisocyanates may have an aliphatic hydrocarbon group with 2 to 20 carbon atoms. The aliphatic hydrocarbon group with 2 to 20 carbon atoms may be a divalent aliphatic hydrocarbon group. 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 alkylene end.

[0124] Cyclic alicyclic polyisocyanates are aliphatic polyisocyanates with a cyclic structure. Cyclic alicyclic polyisocyanates have a non-aromatic carbon ring. Cyclic alicyclic polyisocyanates can have an aliphatic hydrocarbon group with 2 to 20 carbon atoms. The description of aliphatic hydrocarbon groups with 2 to 20 carbon atoms follows the same pattern as for acyclic alicyclic polyisocyanates.

[0125] Bridged-ring alicyclic polyisocyanates are polycyclic compounds with bridging structures formed by the use of methylene groups, etc. Bridged-ring alicyclic polyisocyanates can have aliphatic hydrocarbon groups with 2 to 20 carbon atoms. The description of aliphatic hydrocarbon groups with 2 to 20 carbon atoms follows the same approach as for acyclic alicyclic polyisocyanates.

[0126] The raw material isocyanate can also be a derivative of the raw material isocyanate. Examples of derivatives include isocyanurate derivatives, urethane derivatives, polyol derivatives, biuret derivatives, urea derivatives, oxadiazine trione derivatives, carbodiimide derivatives, urea dione derivatives, and urea ketone imine derivatives.

[0127] The raw material isocyanate can be a derivative of polyisocyanate selected from aromatic polyisocyanates, noncyclic aliphatic polyisocyanates, cyclic alicyclic polyisocyanates and bridged cyclic alicyclic polyisocyanates.

[0128] In one embodiment, the raw material isocyanate can be an isocyanurate derivative or a biuret derivative.

[0129] In one approach, the raw material isocyanate can be a noncyclic aliphatic polyisocyanate.

[0130] Examples of raw material isocyanates include: Aromatic polyisocyanates selected from toluene diisocyanate (2,4- or 2,6-toluene diisocyanate or mixtures thereof) (TDI), phenyl diisocyanate (m-phenylene diisocyanate, terephthalene diisocyanate or mixtures thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), 4,4'-bitoluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, phenyldimethyl diisocyanate (1,3- or 1,4-phenyldimethyl diisocyanate or mixtures thereof) (XDI), tetramethylphenyldiisocyanate, etc. Methyl diisocyanate (1,3- or 1,4-tetramethylphenyldimethyl diisocyanate or mixtures thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or mixtures thereof) (NDI), triphenylmethane triisocyanate, tri(isocyanate phenyl) 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 methylhexanoate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate. Cyclic alicyclic polyisocyanates selected from 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylene bis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis(cyclohexyl isocyanate or mixtures thereof). Hydrogenated MDI, methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanate methyl)cyclohexane (1,3- or 1,4-bis(isocyanate methyl)cyclohexane or mixtures thereof), dimeric acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated toluene diisocyanate (hydrogenated TDI), hydrogenated tetramethylphenyl dimethylene diisocyanate (hydrogenated TMXDI); Bridged cyclic alicyclic polyisocyanates are selected from norbornene diisocyanate, norbornane diisocyanate methyl ester, bicycloheptane triisocyanate, diisocyanate methyl bicycloheptane, and di(diisocyanate methyl)tricyclodecane. Compounds selected from the following substances: ;as well as The above-mentioned isocyanates, biuret modified forms, polymers of polyisocyanates (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazine dione derivatives), pentamers, heptamers, etc.), urea carbamate derivatives (e.g., urea carbamate derivatives generated by reacting the above-mentioned polyisocyanates with monohydric or dihydric alcohols), polyol derivatives (e.g., polyol derivatives (alcohol adducts, preferably trimethylolpropane adducts) generated by reacting the above-mentioned polyisocyanates with trihydric alcohols (e.g., trimethylolpropane), etc.), biuret derivatives (e.g., biuret derivatives generated by reacting the above-mentioned polyisocyanates with water or amines), urea derivatives (e.g., urea derivatives generated by reacting the above-mentioned polyisocyanates with diamines), oxadiazine trione derivatives (e.g., oxadiazine triones generated by reacting the above-mentioned polyisocyanates with carbon dioxide), carbodiimide derivatives (carbodiimide derivatives generated by the decarboxylation condensation reaction of the above-mentioned polyisocyanates), urea dione derivatives, urea ketone imide derivatives, etc.

[0131] The average number of isocyanate groups in the raw material isocyanate is 2 or more, preferably 2.5, more preferably 2.9, and for example 3.8 or less. The raw material isocyanate can be a polyisocyanate having multiple isocyanate groups.

[0132] [(B) Synthetic methods for isocyanate derivatives] Therefore, in order to obtain the isocyanate derivative (B), an active hydrogen compound is reacted with a starting isocyanate. The reaction can be carried out in a first-order process or in a stepwise process. For example, if unreacted active hydrogen groups or active hydrogen reactive groups are present in the product, a stepwise synthesis can be carried out. Stepwise reactions are particularly effective when using substituted sugar alcohols with high OH numbers. 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 active hydrogen compound and the starting isocyanate can be combined in such a way that the equivalence ratio (active hydrogen reactive group / active hydrogen group) of the active hydrogen reactive group (isocyanate group) to the active hydrogen group is, for example, 1.2 or more, preferably 1.5 or more, and for example, 2.0 or less.

[0133] [Composition of isocyanate derivatives] The amount of the portion derived from compound (α) relative to the isocyanate derivative (B) can 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.

[0134] The amount of the portion derived from the monomer (α) relative to the isocyanate derivative (B) can be less than 75% by weight, less than 65% by weight, less than 55% by weight, less than 45% by weight, less than 35% by weight, less than 25% by weight, or less than 15% by weight.

[0135] The amount of the portion derived from the hydrocarbon alcohol (α1) 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.

[0136] The amount of the portion derived from the alkyl alcohol (α1) relative to the portion derived from the active hydrogen compound can be less than 75% by weight, less than 65% by weight, less than 55% by weight, less than 45% by weight, less than 35% by weight, less than 25% by weight, or less than 15% by weight.

[0137] The amount of the portion derived from the sugar alcohol / hydroxy acid modifier (α2) relative to the portion derived from the active hydrogen compound can 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.

[0138] The amount of the portion derived from the sugar alcohol / hydroxy acid modifier may be less than 75% by weight, less than 65% by weight, less than 55% by weight, less than 45% by weight, less than 35% by weight, less than 25% by weight, or less than 15% by weight, relative to the portion derived from the active hydrogen compound.

[0139] The amount of the portion derived from cationic active hydrogen compounds (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 active hydrogen compounds.

[0140] The amount of the portion derived from cationic active hydrogen compounds (α3) may be less than 75% by weight, less than 65% by weight, less than 55% by weight, less than 45% by weight, less than 35% by weight, less than 25% by weight, or less than 15% by weight, relative to the portion derived from active hydrogen compounds.

[0141] The amount of the portion derived from other compounds containing active hydrogen (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 other compounds containing active hydrogen (α4).

[0142] The amount of the portion derived from other compounds containing active hydrogen (α4) may be less than 75% by weight, less than 65% by weight, less than 55% by weight, less than 45% by weight, less than 35% by weight, less than 25% by weight, or less than 15% by weight, relative to the portion derived from active hydrogen compounds.

[0143] The amount of the portion derived from the isocyanate derivative (B) can 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).

[0144] The amount of the portion derived from the isocyanate derivative (B) can be less than 75% by weight, less than 65% by weight, less than 55% by weight, less than 45% by weight, less than 35% by weight, less than 25% by weight, or less than 15% by weight.

[0145] [(B) Amount of isocyanate derivative] The amount of isocyanate derivative (B) relative to 100 parts by weight of the non-fluorinated copolymer (A) can 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. The amount of isocyanate derivative (B) relative to 100 parts by weight of the non-fluorinated copolymer (A) can 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.

[0146] [Organosilicon] The water-repellent composition of the present invention preferably contains organosilicon in addition to the hydrophobic monomer (a1). By containing organosilicon, it is possible to achieve both excellent water repellency and anti-slip properties.

[0147] Organosilicon can be a polymer as shown in the following formula: (R) 53 )3Si-O-[-Si(R 51 )2-O-】 a -[-Si(R 51 )2-O-】 b -Si(R) 53 3 (S1).

[0148] [In the formula, R] 51 Each of the following can be independently represented: 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 the following can independently represent a hydrogen atom, an alkyl group with 1 to 40 carbon atoms, an aryl group with 6 to 40 carbon atoms, an alkoxy group with 1 to 40 carbon atoms, or a saturated hydrocarbon group with 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) ranges from 5 to 200. In R 51 and R 53 In this context, alkyl groups with 1 to 40 carbon atoms and aryl groups with 6 to 40 carbon atoms can be unsubstituted or substituted.

[0149] R 51 and R 53 Specific examples include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl; cyclopentyl, cyclohexyl, cycloheptyl; phenyl, tolyl, naphthyl, or groups in which some or all of the hydrogen atoms bonded to these groups are replaced by halogen atoms, amino groups, cyano groups, etc. R 51 and R 53 Methyl or ethyl is preferred.

[0150] In R 51 and R 53 In alkoxy groups, those with 1 to 40 carbon atoms can be either straight-chain or branched. Examples of alkoxy groups with 1 to 40 carbon atoms include methoxy, ethoxy, propoxy, and butoxy.

[0151] Organosilicon can have at least one long-chain hydrocarbon group. For example, R in formula (S1) can be... 51 At least one of them, R 53 At least one of them, or R 51 and R 53Each of them has at least one long-chain hydrocarbon group, or R 51 At least one (e.g., one) is a long-chain hydrocarbon group. The long-chain hydrocarbon group can be a saturated hydrocarbon group with 6 or more, 10 or more, 15 or more, or 20 or more, preferably 10 or more or 23 or more. Here, the hydrocarbon group can be straight-chain or branched, preferably alkyl. Specific examples of hydrocarbon groups include hexyl (6 carbon atoms), octyl (8 carbon atoms), lauryl (12 carbon atoms), myristyl (14 carbon atoms), stearyl (18 carbon atoms), benzyl (22 carbon atoms), trialkyl (23 carbon atoms), creosyl (tetraalkyl, 24 carbon atoms), cetyl (hexadecyl, 26 carbon atoms), lignite (octadecyl, 28 carbon atoms), beeswaxyl (triadecyl, 30 carbon atoms), and tris(dodecyl) (32 carbon atoms).

[0152] From the perspective of ease of industrial manufacture and availability, apart from long-chain hydrocarbon-based R... 51 and R 53 Other than R 51 and R 53 Preferably, it contains hydrogen atoms or methyl groups, more preferably methyl groups.

[0153] a is an integer greater than or equal to 0. From the viewpoint of being easy to manufacture and obtain industrially, a can be less than 40, less than 30, less than 20, and preferably less than 30.

[0154] The sum of a and b is 5 to 200. From the viewpoint of being easy to manufacture, obtain, and operate industrially, the sum of a and b is preferably 10 to 100, more preferably 40 to 60. a can be 0 to 150, for example 1 to 100. The lower limit of b can be 1, 2, or 3, and the upper limit of b can be 150, 10, or 5.

[0155] When a or b is 2 or more, there are multiple Rs. 51 and R 52 They can be the same or different.

[0156] Preferred R 51 With R 53 The basis (e.g., R is represented by the following formula (S2)) 51 R 52 base and R 53 More than 50 mol% of the total (including bases) are methyl.

[0157] The order of repeating units enclosed in a or b is not limited to the order represented in the chemical formula and is arbitrary. That is, organosilicon can be a random polymer or a block polymer.

[0158] For example, organosilicon can be a polymer as shown in the following formula: (R)53 )3Si-O-[-Si(R 51 )2-O-】 a -[-Si(R 51 (R) 52 )-O-】 b -Si(R) 53 3 (S2).

[0159] [In the formula, R] 51 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 40 carbon atoms, an aryl group with 6 to 40 carbon atoms, an alkoxy group with 1 to 40 carbon atoms, or a long-chain hydrocarbon group. R 52 Each can be used independently to represent a long-chain hydrocarbon group. R 53 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 40 carbon atoms, an aryl group with 6 to 40 carbon atoms, an alkoxy group with 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) ranges from 5 to 200. In equation (S2), R 51 and R 53 It may have alkyl groups with 3 to 40 carbon atoms or unsaturated hydrocarbon groups with 6 to 40 carbon atoms (e.g., hydrocarbon groups with aromatic rings), but preferably does not have these groups.

[0160] Examples of organosilicon are as follows. [In the formula, a represents an integer from 0 to 150,] b represents an integer from 1 to 150. (a+b) ranges from 5 to 200. n is an integer from 1 to 36 (preferably n is a long-chain hydrocarbon group). Organosilicones can be synthesized using existing, well-known methods. For example, organosilicones can be obtained by hydrosilylation of an organosilicon with a SiH group to an α-olefin.

[0161] Examples of organosilicones with SiH groups include methyl hydrogen-containing organosilicones with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methyl hydrogen-containing siloxane. Among these, methyl hydrogen-containing organosilicones are preferred from the viewpoint of being easily manufactured and readily available industrially. Hydrogen-containing organosilicones (e.g., methyl hydrogen-containing organosilicones) refer to compounds in which a portion of the side chain of a polydiorganosiloxane is replaced by hydrogen, and the hydrogen atom is directly bonded to the silicon atom. When using hydrogen-containing organosilicones, a catalyst can be used to improve reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine catalysts can be used. As these catalysts, organic acid metal salts are preferred, and as organic acids, fatty acids are preferred. From the viewpoint of excellent operability, zinc stearate, etc., can be used. From the perspective of easily achieving the desired effect, it is preferable to use 10 to 40% of the catalyst relative to the methyl hydrogen-containing organosilicon. Two or more types of amino-modified, epoxy-modified, carboxyl-modified, and methyl hydrogen-containing organosilicones can be mixed. Organosilicones that are all reactive and have film-forming properties are preferred. The term "film-forming property" refers to the fact that after the organosilicon is applied to the fiber surface in an emulsion state, it does not form an oily or gel-like substance, but rather a solid film.

[0162] α-Alkenes are compounds that serve as the source of long-chain hydrocarbon groups in organosilicon compounds. Specific examples of α-alkenes include 1-tridecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-tridecene, and 1-tridodecene.

[0163] The hydrosilylation reaction can be carried out stepwise or in one step with the above-mentioned organosilicon with SiH groups in the presence of a catalyst, depending on the need.

[0164] The amounts of SiH-based organosilicon and α-olefin used in the hydrosilylation reaction can be appropriately selected based on the equivalent SiH group or number-average molecular weight of the SiH-based organosilicon.

[0165] Catalysts used in the hydrosilylation reaction include, for example, compounds of platinum, palladium, etc., with platinum compounds being preferred. Examples of platinum compounds include platinum(IV) chloride.

[0166] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted appropriately. The reaction temperature is, for example, 10–200°C, preferably 50–150°C. At a reaction temperature of 50–150°C, the reaction time is, for example, 3–12 hours.

[0167] The hydrosilylation reaction is preferably carried out under a non-reactive gas atmosphere. Examples of non-reactive gases include nitrogen and argon. The reaction can also be carried out under solvent-free conditions, but a solvent can also be used. Examples of solvents include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0168] (Reactive organosilicon) Organosilicones can include reactive organosilicones. Examples of reactive organosilicones include polysiloxanes with reactive groups on side chains, at single ends, at both ends, or on both sides. However, from the viewpoint of excellent slip resistance and water repellency, it can be a polysiloxane with reactive groups on side chains and / or at both ends. There are no particular limitations on reactive organosilicones as long as they contain reactive groups within the molecule; examples include amino-modified organosilicones, epoxy-modified organosilicones, carboxyl-modified organosilicones, and hydrogen-modified organosilicones. Reactive organosilicones can also be substances in which one or more substituents in formula (S1) or formula (S2) above are replaced by reactive groups.

[0169] Examples of amino-modified organosilicones include substances having an amino group bonded to an organic group directly bonded to a silicon atom. The organic group can be any of an alkylene group or a divalent aromatic group. As an alkylene group, it is preferred that it has 2 or more carbon atoms. As a divalent aromatic group, it is preferred that it has 6 or more carbon atoms. The amino group can be any of a primary amino group, a secondary amino group, or a tertiary amino group. Examples of the organic group bonded with an amino group include: 2-aminoethyl, N-methyl-2-aminoethyl, N,N-dimethyl-2-aminoethyl, N-ethyl-2-aminoethyl, N,N-diethyl-2-aminoethyl, N,N-methylethyl-2-aminoethyl, 3-aminopropyl, N-methyl-3-aminopropyl, N,N-dimethyl-3-aminopropyl, N-ethyl-3-aminopropyl, N,N-diethyl-3-aminopropyl, and N,N-methylethyl-3-aminopropyl. These functional groups can be present on the side chains of polysiloxanes or at the ends.

[0170] Examples of epoxy-modified organosilicones include substances having an epoxy group bonded to an organic group directly bonded to a silicon atom. The organic group can be any of an alkylene group or a divalent aromatic group. In this form, it is typically bonded to the aforementioned organic group in the form of a glycidyl ether. Examples of such functional groups include 3-epoxypropoxypropyl and 2-epoxypropoxyethyl. These functional groups can be present on the side chain of the polysiloxane or at the end.

[0171] Examples of carboxyl-modified organosilicones include substances having a structure in which a carboxyl group is bonded to an organic group directly bonded to a silicon atom. The organic group can be either an alkylene group or a divalent aromatic group. As an alkylene group, it is preferred that it has 2 or more carbon atoms. As a divalent aromatic group, it is preferred that it has 6 or more carbon atoms. Examples of such functional groups include 3-carboxypropyl and 2-carboxyethyl. These functional groups can be present in the side chain or at the end of the polysiloxane.

[0172] (Organosilicon resin) Organosilicon can include organosilicon resins. Organosilicon resins are derived from R3SiO2. 1／2 Unit (M unit), RSiO 3／2 Unit (T unit) and SiO 4／2 The silicone resin is composed of at least one of the units (Q unit), where R is a monovalent alkyl group with 1 to 18 carbon atoms, either linear or branched. Silicone resins composed only of M units and silicone resins composed only of Q units are excluded. From the viewpoint of maximizing the effects of the present invention, silicone resin (B) is preferably free of R₂SiO₂. 2／2 Unit (D unit).

[0173] The silicone resin is preferably in a sol state. Examples of R include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, decyl, cetyl, stearyl, etc., but considering the stability of silicone resin (B) in the sol state, the availability and price of raw materials, R is preferably methyl, and particularly preferably more than 90% of all R is methyl. However, R can also contain different types of groups.

[0174] In organosilicon resin containing R2SiO 2／2 When D-units are used, the low slippage property of the water-repellent composition may be compromised. Additionally, silicone resins composed solely of Q-units may hinder the water-repellent properties of the composition.

[0175] The structure of the silicone resin can be exemplified as (i) composed of M units and Q units, (ii) composed of M units, T units and Q units, (iii) composed of M units and T units, (iv) composed of T units and Q units, and (v) composed only of T units. Preferably, it is the silicone resin composed of (i) M units and Q units and (v) composed only of T units. In the silicone resin composed of (i) M units and Q units, the molar ratio (M / Q) of the M units to the Q units is preferably M / Q = 0.6 to 1.3, more preferably M / Q = 0.8 to 1.1. However, two or more of these silicone resins can also be used together.

[0176] Additionally, silicone resin (B) can contain structural units with hydroxyl groups bonded to silicon atoms. Specifically, (HO)RSiO can be listed as an example. 2／2 Unit or (HO)2RSiO 1／2 Unit, (HO)SiO 3／2 Unit, (HO)2SiO 2／2 Unit, (HO)3SiO 1／2 The unit, a portion of the hydroxyl group, can be an alkoxy group as shown by the RO group.

[0177] Sol containing organosilicon resin can be manufactured as described in Japanese Patent 3852921 by uniformly dispersing and polymerizing an organodisiloxane and a tetraalkoxysilane and their partially hydrolyzed condensates in water containing a surfactant, or by hydrolyzing the silane compounds shown below in water.

[0178] A detailed description is provided of a method for manufacturing silane compounds by hydrolyzing them in water. The raw materials used in this manufacturing process are chlorinated or alkoxy groups, and may contain one, three, or four hydrolyzable groups. Any silane compound containing an alkyl group that meets the above conditions can be used. Examples of usable silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrichlorosilane, isopropyltrimethoxysilane, and isopropyltriethoxysilane. Silane, Butyltrichlorosilane, Butyltrimethoxysilane, Butyltriethoxysilane, Isobutyltrichlorosilane, Isobutyltrimethoxysilane, Isobutyltriethoxysilane, Hexyltrichlorosilane, Hexyltrimethoxysilane, Hexyltriethoxysilane, 2-Ethylhexyltrichlorosilane, 2-Ethylhexyltrimethoxysilane, 2-Ethylhexyltriethoxysilane, Decyltrichlorosilane, Decyltrimethoxysilane, Decyltriethoxysilane, Cetyltrichlorosilane, Cetyltrimethoxysilane, Cetyltrichlorosilane, Cetyltrimethoxysilane, Cetyltrichlorosilane Wax-based triethoxysilane, stearyl trichlorosilane, stearyl trimethoxysilane, stearyl triethoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, dimethylethylchlorosilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylpropylchlorosilane, dimethylpropylmethoxysilane, dimethylpropylethoxysilane, dimethylisopropylchlorosilane, dimethylisopropylmethoxysilane, dimethylisopropylethyl... Silanes that can be used include oxysilanes, dimethylhexylchlorosilane, dimethylhexylmethoxysilane, dimethylhexylethoxysilane, dimethyldecylchlorosilane, dimethyldecylmethoxysilane, dimethyldecylethoxysilane, dimethylcetylchlorosilane, dimethylcetylmethoxysilane, dimethylcetylethoxysilane, dimethylstearylchlorosilane, dimethylstearylmethoxysilane, dimethylstearylethoxysilane, and their partial hydrolysates, but are not limited to these. From the perspectives of operability, ease of distillation removal of byproducts, and ease of obtaining raw materials, methoxysilanes or ethoxysilanes are preferred. Mixtures of one or more of these silane compounds can also be used.

[0179] As a method for hydrolyzing silane compounds in water, conventional methods that are generally known can be used. That is, the method of hydrolyzing the silane compound dropwise into the water while carrying out the hydrolysis reaction, or the method of mixing the water and the silane compound together before carrying out the hydrolysis reaction.

[0180] A hydrolysis catalyst can be used when carrying out the hydrolysis reaction. Existing known catalysts can be used, and both acidic and basic catalysts can be employed. In the case of an acidic catalyst, 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 a basic catalyst, alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate, alkali metal silanodes such as sodium siloxide and potassium silanodes, amines such as triethylamine, diethylamine, and aniline, and ammonia can be used. The amount of catalyst added is preferably adjusted to adjust the pH of the aqueous solution to 2-7 or 7-12. Furthermore, after the reaction is complete, a neutralizing agent can be added as needed to neutralize the acidic or basic catalyst.

[0181] A surfactant can be added to the aqueous solution to disperse the silane compound and the hydrolysis products in the water. There are no particular limitations on the surfactant; anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, and alkyl phosphates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene propylene 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 alkyl imidazolines can be used alone or in combination of two or more. Additionally, substances exhibiting acidity or alkalinity can also serve as hydrolysis catalysts. There are no particular limitations on the amount of surfactant added, but 1 to 50 parts by weight relative to 100 parts by weight of the silane compound is preferred. Less than 1 part by weight will not provide sufficient surfactant effect, while more than 50 parts by weight may impair the water-repellent properties of the agent.

[0182] Hydrolysis catalysts and surfactants can be added to a mixture of water and silane compounds as needed, and the hydrolysis reaction can be carried out at 0–90°C for 10 minutes to 24 hours. Afterwards, a neutralization reaction is performed as needed, thereby obtaining an organosilicon resin. Furthermore, alcohols and neutralizing salts generated as byproducts of the hydrolysis reaction can be removed by vacuum distillation or filtration. Various additives can be incorporated into this organosilicon resin. For example, preservatives and thickeners can be added depending on the intended use.

[0183] (Amount of organosilicon) The amount of organosilicon relative to 100 parts by weight of the non-fluorinated copolymer (A) can 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. The amount of organosilicon relative to 100 parts by weight of the non-fluorinated copolymer (A) can be less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0184] 〔wax〕 The water-repellent composition of the present invention preferably contains wax in addition to the hydrophobic monomer (a1). By containing wax, it is possible to achieve both good water repellency and anti-slip properties. The water-repellent composition of the present invention may contain both organosilicon and wax, or either organosilicon or wax.

[0185] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin waxes (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin waxes, animal and plant waxes, and mineral waxes, with paraffin wax being preferred. Specific examples of compounds constituting the wax include n-alkanes (e.g., tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, triacontane, hexadecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane), and n-olefins (e.g., 1-eicosene, 1-docene, 1-docene, 1-docene, 1-tetradecene, 1-pentane, 1-hexadecene, 1-heptadecene, 1-octadecene, nonacontane, tridecane, hexadecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane). 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 waxes can be 200–2000, for example 250–1500, or 300–1000. They can be used alone or in combination of two or more.

[0186] The melting point of the wax can be above 50°C, above 55°C, above 60°C, above 65°C, or above 70°C, preferably above 55°C, and more preferably above 60°C. The melting point of the wax is determined according to JIS K 2235-1991.

[0187] (Amount of wax) The amount of wax relative to 100 parts by weight of the non-fluorinated copolymer (A) can 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. The amount of wax relative to 100 parts by weight of the non-fluorinated copolymer (A) can be less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0188] [Inorganic particles] The water-repellent composition of the present invention may contain inorganic particles. The presence of inorganic particles imparts better water repellency and anti-slip properties. The inorganic particles may be aluminum compounds (e.g., alumina), silicon compounds (e.g., silicon dioxide), titanium compounds, etc. They may be used alone or in combination of two or more. The inorganic particles may undergo a hydrophilic surface treatment or a hydrophobic surface treatment.

[0189] The average primary particle size of the inorganic particles can 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 size of the inorganic particles can be less than 600 nm, less than 400 nm, less than 200 nm, less than 100 nm, less than 40 nm, less than 37.5 nm, less than 35 nm, less than 32.5 nm, less than 30 nm, less than 27.5 nm, less than 25 nm, or less than 22.5 nm, preferably less than 40 nm. Being within the above ranges allows for both good water repellency and slip resistance. The average primary particle size can be determined using a microscope (scanning electron microscope or transmission electron microscope). Specifically, the raw material is observed from above at any magnification using a microscope. Then, when the particle shape is spherical, its diameter is considered the particle size; when it is non-spherical, the average of its longest and shortest diameters is considered the particle size. Repeat the process of measuring the particle size of all particles present in the field of view, then moving the field of view and measuring the particle size again, so as to measure the particle size at more than 10 locations, and take the average value as the average primary particle size.

[0190] (Amount of inorganic particles) The amount of inorganic particles relative to 100 parts by weight of the non-fluorinated copolymer (A) can 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. The amount of inorganic particles relative to 100 parts by weight of the non-fluorinated copolymer (A) can be less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0191] [Liquid medium] The water-repellent composition may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. A mixture of water and an organic solvent is preferred. By containing an organic solvent, both good water repellency and anti-slip properties can be achieved.

[0192] 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 isopropanol), aromatic solvents (e.g., toluene and xylene), and petroleum-based solvents (e.g., alkanes with 5 to 10 carbon atoms, specifically naphtha and kerosene). Water-soluble organic solvents are preferred. Water-soluble organic solvents may contain compounds having at least one hydroxyl group (e.g., alcohols, diols, polyols, ethers of polyols (e.g., monoethers)). They can be used alone or in combination of two or more.

[0193] (Amount of liquid medium) The amount of liquid medium relative to the water-repellent composition can be 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 97% by weight or more. The amount of liquid medium relative to the water-repellent composition can be 99.9% by weight or less, 99% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, or 50% by weight or less.

[0194] The amount of organic solvent relative to the water-repellent composition can be 0.5% by weight or more, 1% by weight or more, 2% by weight or more, 3% by weight or more, 5% by weight or more, 7.5% by weight or more, 10% by weight or more, 12.5% ​​by weight or more, 15% by weight or more, or 20% by weight or more. The amount of organic solvent relative to the water-repellent composition can be 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less.

[0195] The amount of organic solvent relative to the liquid medium can be 1% or more by weight, 3% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, or 40% or more by weight. The amount of organic solvent relative to the liquid medium can be less than 55% by weight, less than 45% by weight, less than 35% by weight, less than 25% by weight, less than 15% by weight, less than 12.5% ​​by weight, less than 7.5% by weight, or less than 5.0% by weight.

[0196] The amount of organic solvent relative to 100 parts by weight of the non-fluorinated copolymer (A) can 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. The amount of organic solvent relative to 100 parts by weight of the non-fluorinated copolymer (A) can be less than 200 parts by weight, less than 175 parts by weight, less than 150 parts by weight, less than 125 parts by weight, less than 100 parts by weight, less than 80 parts by weight, less than 60 parts by weight, less than 40 parts by weight, less than 20 parts by weight, or less than 10 parts by weight.

[0197] The amount of organic solvent relative to 100 parts by weight of water can 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. The amount of organic solvent relative to 100 parts by weight of water can be less than 100 parts by weight, less than 75 parts by weight, less than 50 parts by weight, less than 25 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0198] [Dispersant] The water-repellent composition may contain a dispersant for improving the dispersibility of the non-fluorinated copolymer (A). The dispersant may be a polymeric dispersant, preferably a hydrophilic polymeric dispersant. Polyvinylpyrrolidone, polyvinyl alcohol, polyglycerol, polyacrylate, etc., may be used as dispersants. They may be used alone or in combination of two or more.

[0199] (Amount of dispersant) The amount of dispersant relative to 100 parts by weight of the non-fluorinated copolymer (A) can 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. The amount of dispersant relative to 100 parts by weight of the non-fluorinated copolymer (A) can 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.

[0200] [surfactants] The water-repellent composition preferably contains a surfactant. The surfactant in the water-repellent composition may include a nonionic surfactant. By containing a surfactant, both good water repellency and anti-slip properties can be achieved. The surfactant may further contain one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. A combination of nonionic and cationic surfactants is preferred.

[0201] (Nonionic surfactant) Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0202] Examples of ethers include compounds having oxyalkylene groups (preferably polyoxyethylene groups).

[0203] Examples of esters include esters of alcohols and fatty acids. Examples of alcohols include alcohols with 1 to 6 carbon atoms (especially 2 to 5 carbon atoms) and 1 to 50 carbon atoms (especially 10 to 30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids include saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0204] Examples of ester ethers include compounds formed by the esterification of alkyl oxidases (especially ethylene oxide) with alcohols and fatty acids. Examples of alcohols include alcohols with 1 to 6 members (especially 2 to 5 members) and 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids include saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0205] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides can be monoalkanolamides or dialkanolamides. Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines can be alkanols with 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0206] Polyols can be alcohols with 2 to 5 carbon atoms and 10 to 30 carbon atoms.

[0207] The amine oxide can be an oxide of an amine (secondary amine or preferably tertiary amine) (e.g., having 5 to 50 carbon atoms).

[0208] The nonionic surfactant is preferably a nonionic surfactant having an oxoalkylene group (preferably polyoxoethylene). The number of carbon atoms in the oxoalkylene group is preferably 2 to 10. The number of oxoalkylene groups in the molecule of the nonionic surfactant is usually preferably 2 to 100.

[0209] The nonionic surfactant is selected from ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic surfactant with oxyalkylene oxides.

[0210] Nonionic surfactants can 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 glycol adducts, etc. Preferably, the alkylene oxide adduct portion and the polyalkylene glycol portion are substances with the structure of polyoxyethylene (POE), polyoxypropylene (POP), or POE / POP copolymers (which can be random copolymers or block copolymers).

[0211] In addition, considering environmental issues (biodegradability, endocrine disruptors, etc.), nonionic surfactants are preferably those without aromatic groups.

[0212] Nonionic surfactants can be of the following formula: R 1 O-(CH2CH2O) p - (R) 2 O) q -R 3 The compound shown.

[0213] [In the formula, R] 1 It is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group. R 2 Each, independently, identically, or differently, is an alkylene group having 3 or more carbon atoms (e.g., 3–10). R 3 It consists of hydrogen atoms, alkyl groups having 1 to 22 carbon atoms, or alkenyl groups having 2 to 22 carbon atoms. p is a number greater than or equal to 2. q is a number that is 0 or greater than 1. R 1 Preferably, the number of carbon atoms is 8–20, particularly 10–18. As R… 1 Preferred specific examples may include lauryl, dodecyl, and oleyl.

[0214] R 2 Examples include propylidene and butylidene.

[0215] In nonionic surfactants, p can be a number greater than 3 (e.g., 5–200). q can be a number greater than 2 (e.g., 5–200). That is, -(R 2 O) q - It can form polyoxyalkylene chains.

[0216] Nonionic surfactants can be polyoxyethylene alkylene ethers with a central hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (especially a polyoxyalkylene chain). Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, with oxypropylene chains being preferred.

[0217] Specific examples of nonionic surfactants include: ethylene oxide with hexylphenol, isooctylphenol, hexadecyl alcohol, oleic acid, and alkanes (C64- ... 12 -C 16 Thiols, sorbitol monofatty acids (C7-C5) 19 ) or alkyl (C 12 -C 18 Condensation products of amines, etc.

[0218] The proportion of polyoxyethylene blocks relative to the molecular weight of the nonionic surfactant (polymer) can be 5 to 80% by weight, for example 30 to 75% by weight, especially 40 to 70% by weight.

[0219] The average molecular weight of nonionic surfactants is typically 300 to 5,000, for example, 500 to 3,000.

[0220] Nonionic surfactants can be mixtures of compounds with an HLB (hydrophilic-hydrophobic balance) of less than 15 (especially less than 5) and compounds with an HLB of 15 or more. Examples of compounds with an HLB of less than 15 include sorbitan fatty acid esters. Examples of compounds with an HLB of 15 or more include polyoxyethylene alkyl ethers. The weight ratio of compounds with an HLB of less than 15 to compounds with an HLB of 15 or more is 90:10 to 20:80, for example, 85:15 to 55:45.

[0221] Nonionic surfactants can be a single type or a mixture of two or more types.

[0222] (Catonic surfactants) Cationic surfactants are preferably compounds that do not have amide groups.

[0223] Cationic surfactants can be amine salts, quaternary ammonium salts, or oxyethylidene addition ammonium salts. Specific examples of cationic surfactants are not particularly limited, but can include amine salts such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline, as well as quaternary ammonium salts such as alkyl trimethylammonium salts, dialkyl dimethylammonium salts, alkyl dimethyl benzylammonium salts, pyridinium salts, alkyl isoquinoline onion salts, and benzyl chloride.

[0224] Preferred examples of cationic surfactants include compound R. 21 -N +(-R) 22 (-R) 23 (-R) 24 )X － .

[0225] [In the formula, R] 21 R 22 R 23 and -R 24 [X is a hydrocarbon group with 1 to 40 carbon atoms, and X is an anionic group.] R 21 R 22 R 23 and R 24 Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, palmityl). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid, acetic acid).

[0226] Cationic surfactants are particularly preferred monoalkyltrimethylammonium salts (alkyl groups have 4 to 40 carbon atoms).

[0227] Cationic surfactants are preferably ammonium salts. Cationic surfactants can be of the following formula: R 1 p -N + R 2 q X － The ammonium salt shown.

[0228] [In the formula, R] 1 For C12 and above (e.g., C 12 ~C 50 Straight-chain and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 Alkyl, benzyl, or polyoxyethylene (with an oxyethylene number of, for example, 1 (especially 2, especially 3) to 50) of H or C1 to 4 (particularly preferred CH3, C2H5), X is a halogen atom, a C1-C4 fatty acid salt group. p is 1 or 2, q is 2 or 3, and p + q = 4. R 1 The number of carbon atoms can be 12 to 50, for example 12 to 30.

[0229] Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl di(hydrogen polyoxyethylene)ammonium chloride, benzyldodecyl di(hydrogen polyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0230] Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonyl fatty acid salts, N-acyl amino acid type surfactants, phosphate monoester or diester type surfactants, and sulfosuccinates.

[0231] Examples of amphoteric surfactants include alanine-based surfactants, imidazoline betaines, amide betaines, and acetate betaines. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amide propyl dimethylaminoacetic acid betaine.

[0232] Among surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants can each be one type or a combination of two or more types.

[0233] (Amount of surfactant) The amount of surfactant relative to 100 parts by weight of the non-fluorinated copolymer (A) can 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. The amount of surfactant relative to 100 parts by weight of the non-fluorinated copolymer (A) can be less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0234] The amount of cationic surfactant relative to the total amount of surfactant can be 5% by weight or more, preferably 10% by weight or more, and more preferably 20% by weight or more. The weight ratio of nonionic surfactant to cationic surfactant is preferably 95:5 to 20:80, and more preferably 85:15 to 40:60.

[0235] The amount of cationic surfactant relative to 100 parts by weight of water-repellent resin can be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight. The total amount of surfactant relative to 100 parts by weight of water-repellent resin can be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight.

[0236] [Curing agent] The water-repellent composition may contain a curing agent (an active hydrogen reactive compound or a compound containing active hydrogen). The curing agent may be added to the water-repellent composition after polymerization to obtain the non-fluorinated copolymer (A).

[0237] The curing agent (crosslinking agent) in the water-repellent composition enables the non-fluorinated copolymer (A) to cure well. The curing agent can be an active hydrogen reactive compound or a compound containing active hydrogen that reacts with the active hydrogen or active hydrogen reactive groups present in the non-fluorinated copolymer (A). Examples of active hydrogen reactive compounds include polyisocyanate compounds, epoxy compounds, chloromethyl compounds, carboxyl compounds, and acylhydrazine compounds. Examples of compounds containing active hydrogen include hydroxyl compounds, amino compounds, carboxyl compounds, ketone compounds, acylhydrazine compounds, and melamine compounds.

[0238] The curing agent can 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 their derivatives.

[0239] 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, 1,03-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methylhexanoate; as well as lysine ester triisocyanate, 1,4,8-octyl triisocyanate, 1,6,11-undecyl triisocyanate, 1,8-diisocyanate-4-methyl octyl isocyanate, 1,3,6-hexyl triisocyanate, and 2,5,7-trimethyl-1,8-diisocyanate-5-methyl octyl isocyanate, etc. They can be used individually or in combination of two or more.

[0240] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-cyclohexyl triisocyanate. They can be used alone or in combination of two or more.

[0241] 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-phenylenedimethylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyano-1-methylethyl)benzene (tetramethylphenylenedimethylene diisocyanate) or mixtures thereof, and 1,3,5-triisocyanomethylbenzene. They can be used alone or in combination of two or more.

[0242] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, terephthalene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or mixtures thereof, 2,4- or 2,6-toluene diisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, etc. They can be used alone or in combination of two or more.

[0243] Examples of polyisocyanate derivatives include dimers, trimers, biurets, urethanes, carbodiimides, urea diketones, urea ketimides, isocyanurates, iminooxadiazine diketones, and many other derivatives of the aforementioned polyisocyanate compounds. They can be used alone or in combination of two or more.

[0244] These polyisocyanates can be used in one or in combination of two or more.

[0245] As a polyisocyanate compound, it is preferable to use a compound in which the isocyanate group of the polyisocyanate compound is capped by a capping agent, i.e., a capped polyisocyanate compound (capped isocyanate). Capped polyisocyanate compounds are preferred because they are relatively stable even in aqueous solutions and can be used in the same solution as the water-repellent composition.

[0246] End-capping agents are used to seal free isocyanate groups. End-capped polyisocyanate compounds can be regenerated by heating to, for example, above 100°C or above 130°C, thereby readily reacting with hydroxyl groups. Examples of end-capping 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.

[0247] Epoxides are compounds that have epoxy groups. Examples of epoxy compounds include those with polyoxyalkylene groups, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether, etc.

[0248] Chloromethyl compounds are compounds containing a chloromethyl group. Examples of chloromethyl compounds include chloromethyl polystyrene.

[0249] Carboxyl-containing compounds are compounds that contain a carboxyl group. Examples of carboxyl-containing compounds include (poly)acrylic acid and (poly)methacrylic acid.

[0250] Specific examples of ketone-containing compounds include (poly)diacetone acrylamide and diacetone alcohol.

[0251] Specific examples of acylhydrazide compounds include hydrazine, carbazide, and adipic hydrazide.

[0252] Specific examples of melamine compounds include melamine resins and methylated melamine resins.

[0253] (Amount of curing agent) The amount of curing agent relative to 100 parts by weight of the non-fluorinated copolymer (A) can 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. The amount of curing agent relative to 100 parts by weight of the non-fluorinated copolymer (A) can 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.

[0254] The organosilicones, waxes, inorganic particles, liquid media, dispersants, surfactants or curing agents listed above may be added after the manufacture of the non-fluorinated copolymer (A), or the monomers of the non-fluorinated copolymer (A) may be polymerized in the presence of the organosilicones, waxes, inorganic particles, liquid media, dispersants, surfactants or curing agents listed above to manufacture the non-fluorinated copolymer (A).

[0255] [Other ingredients] The water-repellent composition may contain other ingredients besides those mentioned above. Other ingredients may be added after the manufacture of the non-fluorinated copolymer (A). Examples of other ingredients include water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorants, fragrances, etc. They may be used alone or in combination of two or more. In addition to the above-mentioned ingredients, other components include texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying speed regulators, crosslinking agents, film-forming aids, solubilizers, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoamers, anti-shrinkage agents, anti-wrinkle agents for clothing, shape retention agents, drape retention agents, ironing improvers, whitening agents, bleaching agents, fabric softening clay, anti-migration agents such as polyvinylpyrrolidone, polymeric dispersants, stain removers, scum dispersants, and 4,4-bis(2-sulfostylenyl)biphenyl disodium (TINOPLAL, manufactured by CIBA SPECIALTY CHEMICALS). Fluorescent whitening agents such as CBS-X, dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, detergents, enzymes such as cellulase, amylase, protease, lipase, and keratinase used as fiber surface modifiers, defoamers, silk protein powder that imparts moisture absorption and release properties to silk, their surface modifiers, and emulsion dispersions. Specifically, these can be combined with K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (for wool), SILKGEN G Soluble S (ICHIMARU PHARCOS), nonionic polymers composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units, such as FR627 manufactured by Muyo Chemical Industry and SRC-1 manufactured by Clariant Japan, etc. These can be used alone or in combination of two or more.

[0256] (Antistatic agent) Examples of antistatic agents include: quaternary ammonium salts, pyridinium salts, and cationic antistatic agents with cationic functional groups such as primary, secondary, and tertiary amine groups; anionic antistatic agents with anionic functional groups such as sulfonates or sulfates, phosphonates, and phosphates; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, and alanine and its derivatives; and nonionic antistatic agents such as amino alcohols and their derivatives, glycerol and its derivatives, and polyethylene glycol and its derivatives. Ionically conductive polymers can also be obtained by polymerization or copolymerization of monomers with these cationic, anionic, and amphoteric ionic conductive groups. They can be used alone or in combination of two or more.

[0257] (Antibacterial and antifungal agent) An antibacterial and antifungal agent is an antibacterial and antifungal agent that inhibits the growth of microorganisms such as fungi, preferably both fungi and bacteria. There are no particular limitations on the antibacterial and antifungal agent, and the following commonly used antibacterial and antifungal agents listed in the Journal of the Japanese Society for Antimicrobial and Antifungal 1998 VOL.26 can be used.

[0258] Examples can be listed: Amine systems such as bis(3-aminopropyl)dodecylamine (trialkyltriamine); Alcohols including ethyl alcohol, isopropyl alcohol, propyl alcohol, tris(hydroxymethyl)nitromethane, 1,1,1-trichloro-2-methyl-2-propanol, and 2-bromo-2-nitropropane-1,3-diol (Bronopol). Aldehydes such as 1,5-pentanediol (glutaraldehyde), formaldehyde, and α-bromolactinamic aldehyde; Isothiazolinones such as 2-n-octyl-4-isothiazolin-3-one (Skane M-8), 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one (Kathon CG, NS-500W), 1,2-benzisothiazolinone-3 (BIT), and N-n-butyl-1,2-benzisothiazolinone-3 (n-butylBIT) are all isothiazolinone-based products. Isothiocyanate series such as allyl isothiocyanate, Imidazole series such as 2-(4-thiazolyl)-benzimidazole (thiazolyl, TBZ), methyl-2-benzimidazole carbamate (2-benzimidazole carbamate, Preventol BCM); Ester systems such as glyceryl laurate (Lauricidin, Glycerol laurate, monoglyceride); Oxazolidine derivatives such as 4,4-dimethyl-1,3-oxazolidine (BIOBAN CS-1135, Oxazin A), Carbanilide series of 3,4,4'-trichlorocarbanilide, 4,4'-dichloro-3-(3-fluoromethyl)-carboaniline, etc. Carbamate systems such as 3-iodo-2-propynyl butylcarbamate (Glycacil), The carboxylic acid system includes benzoic acid (benzoic acid, benzoic acid), hex-2,4-dienoic acid (sorbic acid, 2-propynylacrylic acid), octanoic acid, propionic acid, undecylenic acid (10-undecylenic acid), potassium 2,4-hexadienoate (potassium sorbate, potassium 2-propenylacrylate), potassium propionate, calcium propionate, sodium benzoate, sodium propionate, bis(2-carboxyphenylperoxycarboxylic acid)dihydro(2-)magnesium phthalate, and zinc undecylenate, etc. Quinoline series such as 8-hydroxyquinoline and bis(8-hydroxyquinoline) copper (quinoline copper, Oxine-copper, 8-quinolinol-copper); Sulfide systems of bis(dimethylthiocarbamoyl) disulfide (TMTD, thiuram, etc.); Diphenyl ethers such as 2,4,4'-trichloro-2'-hydroxydiphenyl ethers (triclosan, Irgasan DP300, etc.); Sulfonamides such as N,N-dimethyl-N'-(fluorodichloromethylthio)-N"-benzenesulfonamide (benzenesulfonamide, Preventol A4-S), N-dichlorofluoromethylthio-N',N'-dimethyl-N-p-toluenesulfonamide (triflamide, Preventol A5), etc. Protein systems such as protamine (protamine, protamine breakdown product, nucleoprotein) and egg lysozyme (protein lysozyme); Thiazole series such as 2-(4-thiocyanomethylthio)benzothiazole (benzothiazole); Thiocarbamates such as sodium N-methyldithiocarbamate (Metamsodium); Hexahydro-1,3,5-trihydroxyethyltriazine (BIOBAN GK, triazine); Triazine series including CAVINON (100,200) and α-[2-(4-chlorophenyl)ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol (tebuconazole); The tolphenone series of 4-isopropyl-2-hydroxycyclohepta-2,4,6-trien-1-one (ribaithiol, β-thuja succinate, etc.); Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile (tetrachloroisophthalonitrile) and 1,2-dibromo-2,4-dicyanobutane (TEKTAMER38); Biguanides such as 1,1'-(hexamethylene bis[5-(4-chlorophenyl)biguanide] digluconate (chlorhexidine gluconate), bis(p-chlorophenylbiguanide) hexane dihydrochloride (chlorhexidine hydrochloride), etc.; Hydantoin series including 1-bromo-3-chloro-5,5'-dimethylhydantoin (Dantobrom), 1,3-bis(hydroxymethyl)-5,5'-dimethylhydantoin (Glydant, Dantogard), etc. Pyridine series including sodium pyridyl mercapto-1-oxide (pyridylthioonium sodium), zinc bis(2-pyridyl mercapto-1-oxide) (pyridylthioonium zinc, pyridylthionone zinc, ZPT), 2,3,5,6-tetrachloro-4-(methanesulfonyl)pyridine (Densil), copper bis(2-pyridyl mercapto-oxide) (pyridylthioonium copper, pyridylthionone copper, CuPT), etc. Phenolic compounds including 2-isopropyl-5-methylphenol (thymol, 2-Isopropyl-5-methylphenol), 3-methyl-4-isopropylphenol (isopropylmethylphenol, Piozole), o-phenylphenol (OPP, o-Phenylphenol), phenol (Phenol, carbolic acid), butyl paraben (butylparaben), ethyl paraben (ethylparaben), methyl paraben (methylparaben), propyl paraben (propylparaben), m-Methylphenol, o-Methylphenol, p-Methylphenol, o-Phenylsodium phenoxide, 2-phenyl-4-chlorophenol (chlorophenol), p-Chlorophenol, 4-chloro-3,5-dimethylphenol (p-chloroxylenol), and 2-methyl-3-chlorophenol (p-chlorom-cresol); Phthalate series including N-(fluorodichloromethylthio)phthalimide (Fluorfolpet, PREVENTOL A3); Peptide systems such as ε-poly-L-lysine (polylysine, ε-polylysine); Morpholine series such as 4-(2-nitrobutyl)morpholine / 4,4'-(2-nitrotrimethylene)bismorpholine (BIOBAN P-1487); Iodine-based compounds include diiodomethyl-p-trylsulfone, polyvinylpyrolidone iodide, isodine, p-Chlorophenyl-3-iodopropagyl formal, and 3-bromo-2,3-diiodo-2-propenyl ethyl carbonate (Sunplus). Sodium hypochlorite, sodium dichloroisocyanurate, trichloroisocyanuric acid, and other chlorine-based compounds; Peroxide systems including hydrogen peroxide, chlorine dioxide (stabilized chlorine dioxide, BIOTALK), and peracetic acid; Metal salt systems including copper naphthenate, silver / zirconium phosphate (Novaron AG300), silver chloride / titanium oxide, silver-zinc / calcium phosphate (Silver-Zinc / Calciumphosphate, Silver Ace), silver-zinc / zeolite (Silver-Zinc / Zeolite), zinc oxide, silver / zirconium phosphate (Novaron AGZ330), and N-stearoyl-L-glutamic acid silver copper salt (Holon Killer); Antibiotics such as 1-L-(1,3,5 / 2,4)-1,5-diamino-4-O-(2,5-dideoxy-α-D-glucopyranosyl)-2,3-cyclohexanol (ST-7); Oxide systems of ethylene oxide (EO, Ethylene oxide), propylene oxide (PO, Propylene oxide), etc. 4,4'-(tetramethylenedicarbonyldiamino)bis(1-decylpyridinium bromide) (dimer 135), decyl dimethyl benzyl ammonium chloride (benzyl chloride), didecyl dimethyl ammonium chloride (Didecyldimethylammonium chloride, Bardac 2250 / 80), diisobutylphenoxyethoxydimethyl benzyl ammonium chloride (benzyl chloride, Hyamine 1622), hexadecyltrimethylammonium bromide (cetrimide, CTAB, cetrimonium bromide), N,N'-hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide) (dimer 38), N-alkyl-N,N-dimethyl-N-benzyl ammonium chloride (benzyl chloride, Hyamine) Quaternary ammonium salts of 3500J, N-decyl-N-isononyl-N,N'-dimethylammonium chloride (Bardac170P), 5-(trimethoxysilyl)propyldimethyloctadecylammonium (DC-5700), hexadecylpyridinium chloride (cetylpyridinium chloride), etc. Sugars such as β-1,4-poly-D-glucosamine (chitosan); Urea-based agents such as N'-(3,4-dichlorophenyl)-N,N-dimethylurea (Diuron, DCMU, Preventol A6, etc.) are particularly preferred. Especially preferred are isothiazolin-based antibacterial and antifungal agents such as 2-n-octyl-4-isothiazolin-3-one (Skane M6), mixtures of 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolinone-3 (BIT), and N-n-butyl-1,2-benzisothiazolinone-3 (BBIT).

[0259] Particularly preferred are isothiazolin-based antibacterial and antifungal agents such as 2-n-octyl-4-isothiazolin-3-one, mixtures of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolinone-3 (BIT), and N-n-butyl-1,2-benzisothiazolinone-3 (BBIT). These antibacterial and antifungal agents can be used alone or in combination of two or more.

[0260] Relative to the overall water-repellent composition, the amount of antibacterial and antifungal agent, based on the concentration of the active ingredient, can be 1.5 ppm or more, 7.5 ppm or more, 30 ppm or more, 75 ppm or more, or 100 ppm or more, and can be less than 600 ppm, less than 450 ppm, less than 300 ppm, less than 200 ppm, less than 150 ppm, or less than 100 ppm. For example, relative to the overall water-repellent composition, the amount of antibacterial and antifungal agent can be 1.5 to 450 ppm, preferably 7.5 to 300 ppm, and particularly preferably 75 to 150 ppm.

[0261] The amount of antibacterial and antifungal agent relative to the non-fluorinated copolymer (A) can be 1.5 ppm or more, 7.5 ppm or more, 30 ppm or more, 75 ppm or more, 150 ppm or more, 250 ppm or more, or 300 ppm or more, and can be less than 1500 ppm, less than 1000 ppm, less than 750 ppm, less than 450 ppm, less than 300 ppm, less than 200 ppm, less than 150 ppm, or less than 150 ppm. For example, the amount of antibacterial and antifungal agent relative to the non-fluorinated copolymer (A) can be 4.5 to 1350 ppm, preferably 22.5 to 900 ppm, and particularly preferably 225 to 450 ppm.

[0262] Antibacterial and antifungal agents can be used as preservatives or antimicrobial agents.

[0263] (preservative) Preservatives are mainly used to increase preservative and bactericidal properties, ensuring preservation during long-term storage. Examples of preservatives include isothiazolone organosulfur compounds, benzisothiazolone organosulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol. The amount of preservative relative to the total weight of the water-repellent composition is preferably 0.0001 to 1% by weight. When the amount of preservative is above the lower limit of the above range, the effect of adding preservatives can be sufficiently obtained; when it is below the upper limit, the storage stability of the water-repellent composition is good.

[0264] (Antibacterial agent) Antimicrobial agents are ingredients that inhibit the proliferation of bacteria on fibers, thereby suppressing the production of unpleasant odors caused by microbial decomposition products. Examples of antimicrobial agents include cationic bactericides such as quaternary ammonium salts, zinc bis-(2-pyridylthio-1-oxide), polyhexamethylene biguanide hydrochloride, 8-hydroxyquinoline, and polylysine.

[0265] (UV absorber) Ultraviolet (UV) absorbers are agents that protect against ultraviolet radiation. They absorb UV rays and convert them into infrared or visible light. Examples of UV absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-tert-butyl-4'-methoxybenzoylmethane.

[0266] (Deodorant) Examples of deodorants include clustered dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyl dimethylamine oxide, and aminocarboxylic acid metal complexes (such as the zinc complex of trisodium methylglycine diacetate described in International Publication No. 2012 / 090580).

[0267] (spices) As a fragrance, there are no particular limitations, and a list of fragrance raw materials that can be used can be found in various documents, such as: "Perfume and Flavor Chemicals", Vol. Iand II, Steffen Arctander, Allured Pub. Co. (1994); "Synthetic Fragrance Chemistry and Commercial Knowledge", by Genichi Into, Chemical Industry Daily (1996); "Perfume and Flavor Materials of Natural Origin", Steffen Arctander, Allured Pub. Co. (1994); "Encyclopedia of Fragrance", edited by 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), etc. These documents can be cited as part of the invention in this specification.

[0268] (Amount of other ingredients) The amounts of other components relative to 100 parts by weight of the non-fluorinated copolymer (A) 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. The amounts of other components relative to 100 parts by weight of the non-fluorinated copolymer (A) may be less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0269] <Method for manufacturing water-repellent composition> A method for manufacturing a water-repellent composition may include copolymerizing a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms with a chloride monomer (a2) selected from at least one of vinyl chloride and vinylidene chloride in the presence of an isocyanate derivative (B) to obtain a non-fluorinated copolymer (A). Using this method (hereinafter referred to as the first method), the water-repellent composition of the present invention can be obtained.

[0270] In one embodiment, a method for manufacturing the water-repellent composition includes the step of copolymerizing a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms with a chloride monomer (a2) selected from at least one of vinyl chloride and vinylidene chloride in the presence of an isocyanate derivative (B), a surfactant, and a liquid medium to obtain a non-fluorinated copolymer (A). Using this method, the water-repellent composition of the present invention can be obtained.

[0271] Examples of polymerization methods include suspension polymerization and emulsion polymerization. From the viewpoint of obtaining an emulsion of a non-fluorinated copolymer (A), emulsion polymerization can be cited.

[0272] In the case of emulsion polymerization, all or part of the above monomers (specifically, hydrophobic monomers having hydrocarbon groups with 2 to 40 carbon atoms (a1), chloride monomers selected from at least one of vinyl chloride and vinylidene chloride (a2), monomers containing cyclic hydrocarbon groups as needed (a3), crosslinking monomers as needed (a4), and other monomers as needed (a5)) are mixed with isocyanate derivatives (B), surfactants, and liquid media to prepare a mixture.

[0273] The surfactant proportion may be, for example, 1 part or more, preferably 3 parts or more, and for example, 10 parts or less, preferably 5 parts or less, relative to the total amount of monomers (specifically, hydrophobic monomers having hydrocarbon groups having 2 to 40 carbon atoms (a1), chloride monomers selected from at least one of vinyl chloride and vinylidene chloride (a2), monomers containing cyclic hydrocarbon groups as needed (a3), crosslinking monomers as needed (a4), and other monomers as needed (a5), the same below).

[0274] The proportion of the liquid medium relative to 100 parts by weight of the monomer can 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. The liquid medium can be any of the substances listed above. For example, the liquid medium can be water. In emulsion polymerization, an organic solvent can be further added. The liquid media listed above can be used as the organic solvent. The organic solvent can be a water-soluble glycol-based solvent, such as ethylene glycol or propylene glycol.

[0275] In emulsion polymerization, the organic acids listed above may also be added. For example, the organic acid may be a carboxylic acid such as acetic acid. Relative to 100 parts by weight of the total monomer, the organic acid may be, for example, more than 0.01 parts by weight, more than 0.1 parts by weight, and less than 1 part by weight, less than 0.5 parts by weight.

[0276] Next, an emulsifier can be added to the mixture.

[0277] As emulsifiers, well-known emulsifiers can be listed, such as cationic emulsifiers and anionic emulsifiers.

[0278] In addition, the surfactants mentioned above can also be used as emulsifiers.

[0279] Furthermore, the emulsifier may contain a reactive emulsifier. In the case where the emulsifier contains a reactive emulsifier, the non-fluorinated copolymer (A) (the polymer of the aforementioned monomers) becomes a polymer containing structural units derived from the reactive emulsifier.

[0280] When the non-fluorinated copolymer (A) is a polymer containing structural units derived from reactive emulsifiers, the water repellency is not reduced, and the stability of the product of the aqueous dispersion (repellent composition) is improved.

[0281] Reactive emulsifiers are emulsifying and dispersing agents with free radical reactivity, that is, emulsifiers with one or more polymerizable unsaturated groups in their molecules, and are emulsifiers that can copolymerize with the aforementioned monomers.

[0282] Examples of reactive emulsifiers include those disclosed in Japanese Patent Application Publication No. 2017-25440, with the reactive emulsifier shown in the following formula being a preferred example. In the above formula, R 10 It refers to an organic residue with an olefinic unsaturated double bond having 12 to 20 carbon atoms.

[0283] R 11 It indicates an oxoalkylene group with 2 to 10 carbon atoms, preferably an oxoethylene group.

[0284] When the reactive emulsifier is the reactive emulsifier shown in the above formula, the water-repellent property is not reduced, and the stability of the product of the aqueous dispersion (repellent composition) is improved.

[0285] Examples of reactive emulsifiers as shown in the above formula include polyoxyethylene alkylphenol and the like.

[0286] Emulsifiers can be used alone or in combination of two or more.

[0287] The proportion of emulsifier relative to the total amount of monomers (100 parts by weight) can be, for example, 5 parts by weight or more, and for example, 18 parts by weight or less.

[0288] Furthermore, relative to the total amount of isocyanate derivative (B) and nonfluorinated copolymer (A) of 100 parts by weight, the proportion of emulsifier can be, for example, 8 parts by weight or more, and for example, 20 parts by weight or less.

[0289] In addition, the proportion of emulsifier relative to the water-repellent composition can be, for example, 0.5% by weight or more, and for example, 5% by weight or less.

[0290] Next, the above components are mixed, the mixture is stirred, and ultrasound is applied to the mixture to emulsify it.

[0291] As a mixing method, a homogenizer, an ultrasonic homogenizer, a pressure homogenizer, a mixer, a porous membrane pressurization disperser, or other dispersers can be used, with a homogenizer being preferred.

[0292] The stirring conditions can be appropriately set. When using a homogenizer, the speed should be set to, for example, 500 rpm or more and 10,000 rpm or less. The stirring time should be, for example, 0.5 minutes or more and 10 minutes or less, preferably 5 minutes or less. The stirring temperature should be, for example, 50°C or more and 90°C or less.

[0293] Next, if a portion of the monomer was incorporated during the preparation of the above mixture, the remaining portion of the monomer is incorporated into the mixture.

[0294] Next, a polymerization initiator is added to the mixture.

[0295] Examples of polymerization initiators include: azo compounds, such as azobisisobutylamidine dihydrochloride and azobisisobutyronitrile; water-soluble polymerization initiators, such as potassium persulfate, ammonium persulfate, and other persulfate compounds; and oil-soluble polymerization initiators, such as benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl perpentanoate, and diisopropyl percarbonate, etc. Azo compounds are preferred, and azobisisobutyronitrile is more preferred.

[0296] The proportion of polymerization initiator relative to 100 parts by weight of monomer can be, for example, more than 0.01 parts by weight, and can be, for example, less than 10 parts by weight.

[0297] Chain transfer agents can also be added to the mixture as needed.

[0298] Examples of chain transfer agents include mercapto-containing compounds such as lauryl thiols, thioglycols, and thioglycerols (especially alkyl thiols with 1 to 30 carbon atoms); inorganic salts such as sodium hypophosphite and sodium bisulfite; lauryl thiols are preferred.

[0299] The proportion of chain transfer agent relative to 100 parts by weight of monomer can be, for example, more than 0.01 parts by weight, and can be, for example, less than 10 parts by weight.

[0300] The mixture is then heated to polymerize the monomers.

[0301] As for heating conditions, the heating temperature can be, for example, above 40°C or below 80°C; in addition, the heating time can be, for example, above 1 hour or below 6 hours.

[0302] This yields an emulsion of non-fluorinated copolymer (A), resulting in a water-repellent composition containing isocyanate derivative (B) and non-fluorinated copolymer (A) (emulsion).

[0303] In the first method, the monomer constituting the above-mentioned non-fluorinated copolymer (A) is polymerized in the presence of the isocyanate derivative (B), but the isocyanate derivative (B) can also be added after the monomer is polymerized (the second method). Alternatively, the monomer can be polymerized in the presence of a surfactant and a liquid medium, followed by the addition of the isocyanate derivative (B) (the third method).

[0304] The third method is identical to the manufacturing method described above, except that the monomers constituting the non-fluorinated copolymer (A) are polymerized in the absence of the isocyanate derivative (B). Combining the non-fluorinated copolymer (A) obtained using the third method with the isocyanate derivative (B) yields the water-repellent composition of the present invention.

[0305] Alternatively, after preparing a non-fluorinated copolymer (A) by polymerizing the monomer, the obtained non-fluorinated copolymer (A) can be combined with an isocyanate derivative (B) (fourth method). Furthermore, after preparing a non-fluorinated copolymer (A) by polymerizing the monomer, the obtained non-fluorinated copolymer (A), an isocyanate derivative (B), a surfactant, and a liquid medium can be combined (fifth method).

[0306] In the fourth and fifth methods, examples of polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

[0307] In the case of solution polymerization, the monomer is dissolved in an organic solvent in the presence of the above-mentioned polymerization initiator, and then heated while stirring after nitrogen purging.

[0308] The above-mentioned polymerization initiator can be used as a polymerization initiator. The proportion of the polymerization initiator relative to 100 parts by weight of the monomer can be, for example, 0.01 parts by weight or more, and can be, for example, 20 parts by weight or less, preferably 10 parts by weight or less.

[0309] Organic solvents can be those listed above for liquid media. Examples of organic solvents include 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), and alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically ethanol, butanol, isopropanol). Water-soluble glycol-based solvents (e.g., ethylene glycol, propylene glycol, etc.) are preferred as organic solvents.

[0310] The proportion of organic solvent relative to 100 parts by weight of monomer can be, for example, 10 parts by weight or more, preferably 50 parts by weight or more, and can be, for example, 2000 parts by weight or less, preferably 1000 parts by weight or less.

[0311] As heating conditions, the heating temperature can be, for example, above 30°C or below 120°C; the heating time can be, for example, above 1 hour or below 10 hours.

[0312] As described above, a non-fluorinated copolymer (A) can be obtained.

[0313] Then, after generating a non-fluorinated copolymer (A) through solution polymerization, the organic solvent is removed, and the non-fluorinated copolymer (A) is co-integrated with the isocyanate derivative (B) into a surfactant and a liquid medium, thereby preparing an emulsion of the non-fluorinated copolymer (A).

[0314] <Uses of the water-repellent composition> Examples of uses of the water-repellent composition of the present invention include external treatment agents (surface treatment agents) or internal treatment agents, repellents (water-repellent agents, oil-repellent agents or water-repellent and oil-repellent agents, etc., especially water-repellent agents), antifouling agents, stain removers, release agents, mold release agents (external mold release agents or internal mold release agents), etc.

[0315] <Method for manufacturing processed products> The method for manufacturing the treated article of the present invention includes the step of applying the water-repellent composition of the present invention to a substrate (particularly a fiber substrate).

[0316] [Processed Products] Examples of substrates treated with the water-repellent composition of the present invention include fiber products, stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, kiln products, plastics, coatings, and plaster. Various examples of fiber products can be listed. Examples include: natural plant and animal 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 cellulose acetate; inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber; or blends thereof. As an example of a substrate treated with the water-repellent composition, a woven fabric will be described in detail.

[0317] (woven fabric) • Manufacturing method of woven fabrics The woven fabric can be obtained by weaving the above-mentioned blended yarns to obtain the base fabric, followed by post-processing and water-repellent finishing. Weaving can be done using known looms or knitting machines, and the preparatory processes before weaving can also use known equipment.

[0318] In addition, the base fabric is first scouring and relaxing in the post-processing stage. Scouring and relaxing can be carried out continuously or in batches at a temperature of 80–130°C. It is generally preferred to carry out the process in batches at a temperature below 100°C, and it is particularly preferred to use a high-pressure liquid flow dyeing machine equipped with nozzles.

[0319] After scouring and relaxation, the knitted fabric is pre-set. Pre-setting is typically done using a needle tenter frame, with a dry heat treatment at 170–200°C for 30–120 seconds. After pre-setting, dyeing is carried out according to standard methods, followed by final setting as needed.

[0320] After post-processing, the woven fabric can be subjected to a water-repellent treatment. In this treatment, an aqueous solution containing a water-repellent agent (which can be the water-repellent agent composition of this invention) is first prepared. Then, based on methods such as padding, spraying, contact roller coating, or slot coating, the post-processed woven fabric is coated with the aqueous solution and subjected to a dry heat treatment at 105–190°C for 30–150 seconds. Depending on the requirements, the aqueous solution may also contain a crosslinking agent, softener, antistatic agent, etc. After the water-repellent treatment, the woven fabric can be further calendered to improve its water-repellent properties.

[0321] Woven fabrics can be used for clothing, especially for uniforms, women's wear, and sportswear.

[0322] •Layered fabric The fabric can also be provided as a laminated fabric in which a moisture-permeable and waterproof layer is provided on one side of the woven fabric of the present invention. The moisture-permeable and waterproof layer can be directly laminated onto the woven fabric, or it can be laminated onto the woven fabric using an adhesive layer. In the case where the laminated fabric of the present invention is used for clothing or the like, it is configured such that the woven side is exposed to rainwater or the like.

[0323] • Breathable waterproof layer A breathable and waterproof layer is a layer that covers one side of a woven fabric and is formed of a resin that is both waterproof and breathable.

[0324] The breathable and waterproof layer can be formed by directly coating the woven fabric with resin (the resin constituting the breathable and waterproof layer), or by laminating it onto one side of the woven fabric using an adhesive layer described later. In this invention, the woven fabric uses a blended interwoven yarn with fine protrusions formed by winding or loosening. Therefore, these protrusions are firmly wrapped around the adhesive layer or the breathable and waterproof layer, thus exhibiting an anchoring effect, making it less likely for the woven fabric and the breathable and waterproof layer to peel off. When using a conventional woven fabric (one whose surface does not adequately maintain the aforementioned protrusions), the anchoring effect may not be sufficiently achieved, and in this case, there is a tendency for the woven fabric and the breathable and waterproof layer to peel off easily.

[0325] The resin constituting the breathable and waterproof layer is not particularly limited, but it is preferably composed of polyurethane resin as the main component, for example, it preferably contains polyurethane resin in a proportion of 80% by weight or more. Polyurethane resin is generally suitable for forming a resin layer with both breathability and waterproofness. Among these, microporous types are preferred when considering breathability; however, in cases where prolonged exposure to rain or repeated washing is anticipated, non-porous types of breathable polyurethane can also be used instead of microporous types.

[0326] As a polyurethane resin, existing known materials can be used, which are obtained by reacting a polyisocyanate component with a polyol component.

[0327] The breathable and waterproof layer can have a microporous structure or a non-porous structure. Furthermore, in the case of a microporous structure, to ensure the desired breathability, the breathable and waterproof layer can contain inorganic micro-powders.

[0328] Examples of inorganic micropowders include those composed of silicon dioxide, aluminum oxide, or titanium dioxide. Furthermore, the average primary particle size of the inorganic micropowder is preferably around 7 to 40 nm. The content of the inorganic micropowder relative to the total amount of the breathable and waterproof layer is preferably 3 to 50% by weight, more preferably 5 to 50% by weight.

[0329] The thickness of the breathable waterproof layer is preferably 5 μm or more, more preferably 10 to 30 μm. When the thickness is within the above range, the balance between waterproofness and breathability is excellent, and it also has advantages in terms of texture or tear strength.

[0330] • Adhesive layer The laminated fabric preferably includes an adhesive layer. That is, the woven fabric and the breathable waterproof layer are preferably laminated using an adhesive layer. The reason for this is as follows. In this invention, as described above, the woven fabric is a fabric with fine protrusions on its surface formed by winding or loosening. Therefore, the protrusions are firmly wrapped with the adhesive layer, thereby exhibiting an anchoring effect, and thus the woven fabric and the breathable waterproof layer are less likely to peel off.

[0331] Furthermore, when the breathable waterproof layer is directly laminated onto the woven fabric using methods such as coating, protrusions on the surface of the woven fabric penetrate the breathable waterproof layer, sometimes resulting in pinholes and decreased water resistance and strength. Additionally, uneven coating can lead to uneven thickness of the breathable waterproof layer. To prevent this, if the surface of the woven fabric is smoothed using processes such as calendering, the number of protrusions or air-retaining layers decreases, which can sometimes reduce water repellency. Therefore, in this invention, it is preferable to laminate the woven fabric and the breathable waterproof layer using an adhesive.

[0332] There are no particular limitations on the type of adhesive used to form the adhesive layer, but an adhesive with excellent compatibility with the breathable and waterproof layer is preferred. For example, if a resin with polyurethane resin as the main component is selected as the resin for forming the breathable and waterproof layer, an adhesive layer composed of a polyurethane-based adhesive is preferred. Polyurethane-based adhesives can be any type of adhesive, such as ether-based, ester-based, or polycarbonate-based adhesives, but from the viewpoint of providing excellent breathability, ether-based adhesives are preferred.

[0333] The adhesive layer can be formed on the entire surface of one side of the woven fabric, or it can be patterned from the viewpoint of moisture permeability or texture. There are no particular limitations on the form of the pattern, and examples include dotted, linear, grid, checkered, and tortoise shell patterns, etc., all of which are preferably evenly distributed throughout.

[0334] The thickness of the adhesive layer is preferably around 10 to 100 μm, more preferably 20 to 80 μm. When the thickness is less than 10 μm, it is difficult to obtain a durable laminated fabric even if the area occupied by the adhesive is increased; when it exceeds 100 μm, there is a tendency for increased manufacturing costs without obtaining better adhesion, so neither is preferred.

[0335] Lining made of fiber fabric In the laminated fabric of the present invention, a lining fiber fabric may also be laminated on the surface of the breathable waterproof layer (the surface of the breathable waterproof layer opposite to the surface of the woven fabric of the present invention). Using the lining fiber fabric protects the breathable waterproof layer, resulting in superior water resistance (water pressure resistance) and strength. Furthermore, by laminating the lining fiber fabric, the overall stretching of the laminated fabric can be suppressed. Therefore, as a result of the stretching of the protrusions of the blended composite yarns caused by post-lamination processing or tension during wear, the reduction of these protrusions can be suppressed, maintaining better water repellency. Moreover, when a lining fiber fabric is laminated, water repellency can be further improved.

[0336] Various woven fabrics and knitted fabrics can be used as lining materials. Among these, knitted fabrics, compared to woven fabrics, tend to have more prominent lines on the surface, resulting in a less flat surface. From the viewpoint of further enhancing the anchoring effect and preventing peeling from the breathable and waterproof layer, knitted fabrics are preferred. In particular, warp-knitted fabrics are preferred because, compared to knitted structures with other structures, their elasticity is suppressed, thus preventing excessively large stitch gaps and enabling more efficient water repellency. Furthermore, warp-knitted fabrics can produce a long base fabric with fewer seams during weaving, allowing for even layering onto the breathable and waterproof layer, which is also a plus.

[0337] The material of the fibers constituting the lining fabric is not particularly limited and can be appropriately selected, but nylon fibers are preferred. This is because nylon fibers typically use acid dyes, making it less prone to the sublimation of disperse dyes into the breathable and waterproof layer, a problem that can occur with disperse dye-based fibers such as polyester. The morphology (long fibers, short fibers, or yarns) or fineness of the constituent fibers of the lining fabric is not particularly limited and can be appropriately selected without compromising the effectiveness of the invention.

[0338] • Characteristics of laminated fabric The laminated fabric exhibits excellent water resistance. As a preferred example of the water resistance of the laminated fabric of the present invention, examples include water levels measured according to the water resistance test specified in JIS L 1092:2009A (low water pressure method) of 10,000 mm or more, preferably 15,000 mm or more, more preferably 16,000 mm or more, and particularly preferably 20,000 mm or more. The upper limit of this water level is not particularly limited, and examples include 50,000 mm or 25,000 mm.

[0339] The laminated fabric exhibits excellent moisture permeability. A preferred example of the moisture permeability of the laminated fabric of this invention is a moisture permeability of 10000 g / m², measured according to the JIS L 1099:2012 B-1 method (potassium acetate method). 2• 24 hours or more, preferably 15000g / m 2 • 24 hours or more, preferably 20000g / m 2 • More than 24 hours. There is no specific upper limit for this moisture permeability; examples include 40,000 g / m². 2 • 24h or 35000g / m 2 •24h•mm.

[0340] The laminated fabric can suppress interlayer delamination between the woven fabric and the breathable waterproof layer. In the laminated fabric of the present invention, preferred examples of peel strength between the woven fabric and the breathable waterproof layer include peel strengths measured according to JIS L 1089 of 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. To achieve peel strength within the above range, for example, a woven fabric that has not undergone calendering can be used, or an adhesive layer can be provided.

[0341] • Manufacturing method of laminated fabric There is no particular limitation on the manufacturing method of the laminated fabric. Examples of manufacturing methods include the first and second manufacturing methods shown below.

[0342] First manufacturing method: includes the process of forming the above-mentioned breathable and waterproof layer by coating the surface of the woven fabric with a resin that constitutes the above-mentioned breathable and waterproof layer.

[0343] The second manufacturing method includes a process of forming an adhesive layer on a woven fabric or a breathable waterproof layer, and a process of bonding the woven fabric to the breathable waterproof layer using the adhesive layer.

[0344] The woven fabric used in the laminated fabric (i.e., the woven fabric of the present invention described above) preferably maintains as many protrusions as possible on the surface of the fabric. For example, when the woven fabric is calendered to facilitate coating processes, the fine protrusions of the blended yarns are flattened into a flat surface, sometimes making it impossible to achieve a specific water droplet rolling angle. Moreover, during calendering, the aforementioned air-retaining layer cannot be adequately maintained, sometimes failing to achieve the desired water repellency. Therefore, it is preferable to thoroughly study the calendering conditions. For example, when calendering the woven fabric, conventional conditions that do not cause the protrusions of the blended yarns to become too low (e.g., temperature above 130°C, linear pressure 200 to 20000 N / cm) can be used. Furthermore, calendering can also be performed without heating.

[0345] In the first manufacturing method, a method for coating the surface of the woven fabric with a resin that forms a breathable and waterproof layer can be exemplified by, for example, a coating method. In the coating method, a doctor blade coater or a comma coater can be used. Furthermore, from the viewpoint of possessing excellent breathability, a wet method is preferred for obtaining the breathable and waterproof layer.

[0346] In the second manufacturing method, a lamination method can be cited as an example of a method for forming an adhesive layer on a woven fabric or a breathable waterproof layer. In the lamination method, the adhesive layer can be formed using a resin solution or by heat melting. First, gaps are provided on the surface of a release material (release paper, release cloth, or release film, etc.), and while adjusting the thickness, a breathable waterproof layer is formed and heat-treated, thereby forming a film by completely reacting a resin composition (e.g., a resin composition containing resin and organic solvent). The release material can be appropriately removed after lamination or curing.

[0347] Then, an adhesive layer is formed on the woven fabric or the breathable waterproof layer. For example, in the method using a resin solution, a two-component curing polyurethane resin solution with a viscosity adjusted to the range of 500 to 5000 mPa·s can be applied to the entire surface or in a pattern. After drying, the adhesive layer is formed, and the woven fabric and the breathable waterproof layer are bonded together using the adhesive layer. The two are then pressed together or heat-pressed together, thereby performing the second manufacturing method.

[0348] On the other hand, in the case of hot melting, a moisture-curing resin that reacts with moisture in the air is preferred, and in practical terms, a resin that melts in a temperature range of approximately 80–150°C is more preferable. In this case, firstly, the hot-melt resin is melted, depending on factors such as the resin's melting point and viscosity at melt. Then, while coating the molten resin onto the woven fabric or the breathable waterproof layer and cooling it at room temperature, it is allowed to cure, forming an adhesive layer. Subsequently, the woven fabric and the breathable waterproof layer are bonded and pressed together using the adhesive layer, thereby performing the second manufacturing method.

[0349] In the manufacturing process, the second manufacturing method is preferred. This is because when using a coating method to laminate a breathable waterproof layer, there is a risk that the breathable waterproof layer may have pinholes due to tiny protrusions on the surface of the woven fabric, which may reduce its water pressure resistance. In addition, when calendering is performed on the woven fabric to form a uniform breathable waterproof layer, the protrusions or air retention layer may be reduced, which may result in the failure to achieve the expected water repellency. This requires a detailed examination of the calendering conditions, and therefore the process itself may sometimes become cumbersome.

[0350] Then, using appropriate methods known to the public, a lining of fibrous fabric is layered on top of the breathable and waterproof layer.

[0351] • Applications of laminated fabric The laminated fabric has excellent water repellency and breathability, and the breathable and waterproof layer will not peel off even in harsh environments. Therefore, it is preferred for use in uniforms, sportswear, outdoor products and other fields used outdoors.

[0352] [Handling Method] The water-repellent composition of the present invention can be applied to a substrate as a treatment agent (especially a surface treatment agent) using existing known methods. This can be achieved by dispersing the water-repellent composition of the present invention in an organic solvent or water for dilution, applying it to the surface of the substrate using known methods such as dip coating, spray coating, or foam coating, and then drying it. After drying, a fibrous article with the solid components of the water-repellent composition adhering to it can be obtained. Alternatively, if desired, it can be applied and cured together with a suitable crosslinking agent. Furthermore, the water-repellent composition of the present invention can be used in combination with various additives such as water-repellent and / or oil-repellent agents, antislip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, antiwrinkle agents, drying speed modifiers, crosslinking agents, film-forming aids, solubilizers, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, and defoamers. Examples of various additives are the same as those described in the "Other Components" section of the above-described water-repellent composition. The concentration of the non-fluorinated copolymer (A) in the treatment agent that comes into contact with the substrate can be varied as appropriate for the application, and can be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

[0353] [Fiber Products] Various examples can be listed for fiber products used as a base material, such as cloth or paper products. Fiber products used as a base material are also called fiber-based materials.

[0354] Examples of textile products include natural plant and animal 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 cellulose acetate; inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber; and blends thereof. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics; clothing-like cloths and carpets; but they can also be made from fibers, yarns, and intermediate fiber products (such as cotton slivers or rovings) that were not yet cloth.

[0355] Examples of paper products include paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, high-yield pulps such as wood pulp, mechanical pulp or thermomechanical pulp, waste paper pulp such as old newspapers, old magazines, old corrugated paper or deinked waste paper, containers made of paper, and molded objects made of paper. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-quality paper, general liner paper and core, neutral pure white roll paper, neutral liner paper, rust-proof liner paper and metal composite 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, and molded paper (molded containers).

[0356] The water-repellent composition can be applied to fibrous articles (e.g., fabrics) by any known method for treating fibrous articles with liquids. The fibrous article can be impregnated with the water-repellent composition, or the solution can be adhered to or sprayed onto the fibrous article. To exhibit water repellency, the treated fibrous article is preferably dried and cured by heating. The heating temperature can be, for example, 100°C–200°C, 100°C–170°C, or 100°C–120°C. In this invention, good performance can be obtained even with low-temperature heating (e.g., 100°C–140°C). In this invention, the heating time can be from 5 seconds to 60 minutes, for example, from 30 seconds to 3 minutes.

[0357] Alternatively, the water-repellent composition can also be applied to fiber products by washing, for example, by washing or by dry cleaning.

[0358] The treated fiber products can be fabrics, including woven fabrics (woven cloth), knitted fabrics (woven fabrics), and nonwoven fabrics, clothing-like fabrics, and carpets, but can also be fiber, yarn, or intermediate fiber products (e.g., slivers or rovings). The water-repellent composition of the present invention is particularly effective in making fiber products (e.g., synthetic fibers) water-repellent.

[0359] The fibers that make up fiber products can be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, or inorganic fibers. One type of fiber can be used alone, or two or more types can be used together.

[0360] 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), press-groundwood pulp (PGW), and thermomechanical pulp (TMP); chemical pulps such as high-content unbleached coniferous kraft pulp (HNKP, N material), bleached coniferous kraft pulp (NBKP, N material, NB material), unbleached hardwood kraft pulp (LUKP, L material), and bleached hardwood kraft pulp (LBKP, L material); waste paper pulps such as deinked pulp (DIP); and semi-chemical pulps such as waste paper pulp (WP) or semi-chemical pulp (CP).

[0361] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, and copolyester; 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.

[0362] Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupro, high wet modulus viscose, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0363] Alternatively, the fibrous product can also be leather. To make the leather hydrophobic and oleophobic, the manufacturing polymer can be applied to the leather as an aqueous solution or aqueous emulsion at various stages of leather processing, such as during the wetting process or the final processing of the leather.

[0364] Alternatively, the fibrous product can also be paper. The manufacturing polymer can be applied to pre-formed paper, or it can be applied at various stages of papermaking, such as during the paper drying process.

[0365] "Treatment" refers to applying the water-repellent composition to a substrate by impregnation, spraying, coating, or other methods. Through treatment, the non-fluorinated 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 its surface. In other words, through treatment, a substrate (e.g., a fiber product) can be obtained with the non-fluorinated copolymer (A) and isocyanate derivative (B) of the water-repellent composition of this invention adhered to it.

[0366] [Pretreatment of fiber products] The fiber products can be pretreated before being treated with the water-repellent composition of the present invention. By pretreating the fiber products, the water-repellent composition can impart excellent durability to the treated fiber products.

[0367] Examples of pretreatment for fiber products include cationization treatment based on reactions with reactive quaternary ammonium salts, anionization treatment such as sulfonation, carboxylation, and phosphorylation, acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment.

[0368] There are no limitations on the method for pretreating fiber products; any existing known method can be used. Alternatively, the pretreatment solution can be dispersed and diluted in an organic solvent or water as needed, and then applied to the surface of the fiber product using known methods such as dip coating, spray coating, or foam coating, followed by drying. The pH and temperature of the pretreatment solution can be adjusted according to the desired level of treatment. As an example of a method for pretreating fiber products, a method using a hydrocarbon-based water-repellent agent will be described in detail.

[0369] Pretreatment methods for fiber products may include imparting a coating of fibers with a material selected from SO3M. 1 (where M) 1The monovalent group (representing a monovalent cation) is shown as -COOM. 2 (where M) 2 The monovalent group (representing a monovalent cation) and -O-P(O) (OX) are shown. 1 (OX) 2 (where X) 1 and X 2 A process of taking at least one functional group (hereinafter sometimes referred to as "specific functional group") of a monovalent group (each independently representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

[0370] As M 1 Examples include H, K, Na, or ammonium ions that may have substituents. As M... 2 Examples include H, K, Na, or ammonium ions that may have substituents. In X 1 or X 2 When the alkyl group is alkyl, it is preferred to be an alkyl group with 1 to 22 carbon atoms, and more preferably an alkyl group with 4 to 12 carbon atoms.

[0371] Fibers containing the aforementioned specific functional groups (hereinafter sometimes referred to as "fibers containing functional groups") can be prepared by, for example, the following methods.

[0372] (i) To attach a compound having the specific functional group described above to a fibrous material. The attachment of the compound may be a state in which a portion of the compound and a portion of the fiber are chemically bonded within a range where the specific functional group remains in sufficient quantity.

[0373] (ii) A fiber in which the aforementioned specific functional groups are directly introduced into the material constituting the fiber.

[0374] In case (i), for example, a functional group-containing fiber can be obtained by treating the fiber material with a pretreatment liquid containing one or more compounds having the aforementioned specific functional groups in a functional group introduction process.

[0375] As raw materials for fiber materials, there are no particular limitations. Examples include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and cellulose acetate; synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, as well as their composite fibers and blended fibers. Fiber materials can take any form, such as fibers (tows, slivers, etc.), silk, woven fabrics (including cross-knitting), woven fabrics (including interwoven fabrics), non-woven fabrics, and paper.

[0376] In this embodiment, from the viewpoint of obtaining a fiber product with good water repellency, it is preferable to use fiber materials containing polyamide and polyester as raw materials, and particularly preferable to use nylon 6, nylon 6,6 and other nylons, polyethylene terephthalate (PET), polyterephthalate trimethyl terephthalate, polylactic acid and other polyesters, as well as blended fibers containing them.

[0377] As mentioned above, it has -SO3M 1 For compounds, phenolic polymers can be used. Examples of such phenolic polymers include materials containing at least one compound represented by the following general formula. [In formula (2), X] 2 Indicates - SO3M 3 (where M) 3 [This refers to a monovalent cation or a group represented by the following general formula, where n is an integer from 20 to 3000.] [In the formula, M] 4 This indicates a monovalent cation. As for the above M 3 Examples include H, K, Na, or ammonium ions that may have substituents.

[0378] As for the above M 4 Examples include H, K, Na, or ammonium ions that may have substituents.

[0379] The compounds represented by the above general formula can be, for example, formaldehyde condensates of phenol sulfonic acid or methyl acetal condensates of sulfonated bisphenol S.

[0380] As mentioned above, it has -COOM 2 Compounds that can be listed include polycarboxylic acid polymers.

[0381] As polycarboxylic acid polymers, polymers synthesized by conventional free radical polymerization methods using monomers such as acrylic acid, methacrylic acid, and maleic acid, or commercially available polymers can be used.

[0382] As a method for manufacturing polycarboxylate polymers, examples include adding a free radical polymerization initiator to an aqueous solution of the aforementioned monomers and / or their salts, and reacting at 30–150°C for 2–5 hours. Alternatively, alcohols such as methanol, ethanol, and isopropanol, or aqueous solvents such as acetone, can be added to the aqueous solution of the aforementioned monomers and / or their salts. Examples of free radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; redox polymerization initiators combining persulfates and sodium bisulfite; hydrogen peroxide; and water-soluble azo polymerization initiators. These free radical polymerization initiators can be used alone or in combination of two or more. Furthermore, during free radical polymerization, chain transfer agents (e.g., octyl mercaptoacetate) can be added to adjust the degree of polymerization.

[0383] In free radical polymerization, in addition to the monomers mentioned above, copolymerizable monomers can also be used. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate; acrylamide; acrylates; and methacrylates. Acrylates and methacrylates preferably have 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 can be used alone or in combination of two or more.

[0384] In polycarboxylate polymers, the carboxyl groups can be free or neutralized by alkali metals or amine compounds. Examples of alkali metals include sodium, potassium, and lithium; examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0385] From the viewpoint that the resulting fiber product has good water repellency, the weight-average molecular weight of the polycarboxylate polymer is preferably 1,000 to 20,000, more preferably 3,000 to 15,000.

[0386] Polycarboxylate polymers can be commercially available products such as "NEOCRYSTAL 770" (manufactured by Nichika Chemical Co., Ltd., trade name) and "SELOPOL PC-300" (manufactured by Sanyo Chemical Co., Ltd., trade name).

[0387] As mentioned above, it has -O-P(O)(OX) 1 (OX) 2 Compounds of which can be listed, for example, phosphate ester compounds represented by the following general formula. [In the formula, X] 1 or X2 The meaning is the same as above, X 3 [Represents alkyl groups with 1 to 22 carbon atoms.] As the aforementioned phosphate ester compounds, phosphate monoesters, diesters, and triesters, as well as mixtures thereof, can be used, wherein the alkyl ester portion is an alkyl group having 1 to 22 carbon atoms.

[0388] From the viewpoint that the resulting fiber products have good water repellency, lauryl phosphate and decyl phosphate are preferred.

[0389] Phosphate compounds can be commercially available products such as "PHOSPHANOL ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name).

[0390] A pretreatment solution containing one or more of the compounds having the specific functional groups described above can be prepared as an aqueous solution of, for example, the aforementioned compounds. Additionally, the pretreatment solution may also contain acids, bases, surfactants, chelating agents, etc.

[0391] Methods for treating fibrous materials using the aforementioned pretreatment solution include, for example, padding, impregnation, spraying, and coating. For padding, methods using padding apparatuses described on pages 396-397 of the *Dictionary of Fiber Dyeing Processing* (Published by Nikkan Kogyo Shimbun, 1949) or pages 256-260 of *Color Dyeing Chemistry III* (Published by Jitsukyo Publishing Co., Ltd., 1975) can be cited. For coating, methods using coating machines described on pages 473-477 of the *Overview of Dyeing and Finishing Equipment* (Published by Kogyo Publishing Co., Ltd., 1956) can be cited. For impregnation, batch dyeing machines described on pages 196-247 of the *Overview of Dyeing and Finishing Equipment* (Published by Kogyo Publishing Co., Ltd., 1956) can be cited, including liquid dyeing machines, airflow dyeing machines, roller dyeing machines, skein dyeing machines, washing dyeing machines, and package dyeing machines. Examples of spray treatment methods include gas spraying, which uses compressed air to atomize the treatment liquid and then blows it out, and gas spraying using hydraulic atomization. The concentration of the treatment liquid and subsequent heat treatment conditions can be appropriately adjusted considering the purpose and performance. Furthermore, if the pretreatment liquid contains water, it is preferable to dry it after attaching it to the fibrous material to remove the water. There are no particular limitations on the drying method; either dry heat or wet heat methods are acceptable. There are also no particular limitations on the drying temperature; for example, drying can be performed at room temperature to 200°C for 10 seconds to several days. If necessary, a heat treatment at 100 to 180°C for approximately 10 seconds to 5 minutes can be performed after drying.

[0392] In addition, when the fiber material is a dyed product, the pretreatment with the pretreatment solution can be carried out before dyeing or in the same bath as dyeing. However, when performing reduction soaping, there is a risk that the adsorbed compounds with the above-mentioned specific functional groups (such as phenolic polymers) may be shed during the process. Therefore, it is preferable to perform the treatment after reduction soaping after dyeing.

[0393] The treatment temperature for immersion can be set to 60–130℃. The treatment time can be set to 5–60 minutes.

[0394] In the functional group introduction process using a pretreatment solution, it is preferable to treat the material with an amount of the compound having the aforementioned specific functional groups in a quantity of 1.0 to 7.0 parts by mass relative to 100 parts by mass of the fiber material. Within this range, a high level of both durable water repellency and texture can be achieved.

[0395] It is preferable to adjust the pH of the pretreatment solution to 3-5. pH adjustment can be achieved using pH adjusters such as acetic acid or malic acid.

[0396] In the pretreatment solution, salts can also be used to more effectively adsorb compounds with the aforementioned specific functional groups onto the fiber material through the salting-out effect. Examples of usable salts include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0397] In the functional group introduction process using a pretreatment solution, it is preferable to remove the over-treated compound containing the aforementioned specific functional groups. Washing with water is an example of such a removal method. By ensuring thorough removal, the obstruction of water repellency can be suppressed during subsequent water-repellent processing, and the texture of the resulting fiber product is improved. Furthermore, it is preferable that the obtained functional group-containing fiber is thoroughly dried before contacting the hydrocarbon-based water-repellent agent.

[0398] (ii) Examples of fibers in which the aforementioned specific functional groups are directly introduced into the materials constituting the fiber include, for example, cationic dyeable polyester (CD-PET).

[0399] From the viewpoint of improving the water repellency of the resulting fiber product, the surface zeta potential of functional group-containing fibers is preferably -100 to -0.1 mV, more preferably -50 to -1 mV. The surface zeta potential of the fiber can be measured, for example, using a zeta potential-particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0400] The implementation methods have been described above, but it should be understood that various changes can be made to the methods and details as long as they do not depart from the spirit and scope of the claimed protection.

[0401] [Example] The following describes specific embodiments of the present invention, but the embodiments are not intended to limit the present invention.

[0402] [Water repellency test] The water repellency of the test treated fabric was evaluated according to the spraying method of JIS-L-1092 (AATCC-22).

[0403] Water repellency is evaluated according to the criteria shown below. A higher score indicates better water repellency.

[0404] 100 No moisture or water droplets were observed adhering to the surface.

[0405] 90 The surface was not wet, but small water droplets were observed to adhere to it.

[0406] 80 Wetting was observed on the surface of each small water droplet.

[0407] 70 Half of the surface showed moisture, and the state of each small wetted cloth was observed.

[0408] 50 The surface was observed to be wet overall.

[0409] 0. Moisture was observed on both the surface and the back side.

[0410] [Washability] The test fabric was washed 20 times according to Appendix F C4M of JIS L 1930 and then dried using a roller (60°C, 30 minutes) to evaluate the water repellency of the dried test fabric.

[0411] [Slippage] According to ISO 13936-2, the test fabric was subjected to a load of 160N with warp slippage, and the seam slippage (mm) was measured. The smaller the seam slippage value, the better the slippage resistance.

[0412] [Preparation of raw materials] (Example of manufacturing an aqueous dispersion containing acrylic polymer) Manufacturing Example 1 Add 30g of water-soluble glycol solvent as an organic solvent, 120g of pure water as a liquid medium, 58.2g of stearyl acrylate (meth)acrylate containing long-chain aliphatic hydrocarbon groups, 2g of dehydrated sorbitol fatty acid ester as a surfactant, 0.1g of acetic acid as an organic acid, 2g of cationic emulsifier, and 6g of polyoxyethylene alkyl ether to a 500ml plastic container. Heat to 80℃, stir at 2000rpm for 1 minute using a homogenizer, and then emulsify and disperse using ultrasound for 15 minutes.

[0413] Next, the mixture was transferred to a 500ml autoclave, purged with nitrogen, and then 0.2g of lauryl mercaptan as a chain transfer agent and 1.8g of vinyl chloride as a comonomer were added. Then, 1g of an azo-containing water-soluble initiator was added as a polymerization initiator, the mixture was heated to 60°C, and reacted for 4 hours to obtain an aqueous dispersion of the acrylic polymer (hydrocarbon-based water-repellent resin). This dispersion was then diluted with pure water to prepare an aqueous dispersion of the hydrocarbon-based water-repellent resin with a solid component concentration of 30% (specifically, an aqueous dispersion containing the hydrocarbon-based water-repellent resin, surfactant, and liquid medium).

[0414] Manufacturing Examples 2 to 8 Except for changing the formulation according to Table 1, the same procedure as in Manufacturing Example 1 was followed to prepare an aqueous dispersion containing an acrylic polymer, a surfactant, and a liquid medium.

[0415] [Table 1] (Example of manufacturing an aqueous dispersion containing polyurethane) Manufacturing Example 9 1. Synthesis of Aliphatic Polyisocyanate Derivatives In a reactor equipped with a thermometer, stirrer, nitrogen inlet pipe, and cooling pipe, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals Co., Ltd., trade name: Takenate 700), 0.25 parts by mass of 2,6-di-tert-butyl-4-methylphenol (also known as butylated hydroxybenzene, BHT, hindered phenolic antioxidant), and 0.25 parts by mass of tetraphenyldipropylene glycol diphosphite (organophosphite, catalyst promoter) were mixed under a nitrogen atmosphere. Then, 10.7 parts by mass of 1,3-butanediol were added to the mixture, and nitrogen was introduced into the liquid phase for 1 hour. Afterward, the mixture was heated to 80°C and reacted for 3 hours, then cooled to 60°C. Then, 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium-2-ethylhexanoate was added as a catalyst for isocyanurate esterification, and the reaction was carried out for 1.5 hours. Subsequently, 0.04 parts by mass of o-toluenesulfonamide were added relative to 100 parts by mass of HDI. The reaction mixture was then passed through a thin-film distillation apparatus (temperature 150°C, vacuum 93.3 Pa) for distillation until the residual HDI monomer content reached below 0.5%, 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 number of 3.0.

[0416] 2. Manufacturing of hydrocarbon-based polyurethanes In a reactor equipped with a stirrer, thermometer, cooler, and nitrogen inlet pipe, 100.20 g of the above-mentioned aliphatic polyisocyanate derivative, 67.60 g of Kalkol 8098 (stearyl alcohol, manufactured by Kao Corporation), a long-chain active hydrogen compound, and 22.30 g of oleyl alcohol were mixed and reacted at 110°C for 4 hours under a nitrogen atmosphere until the concentration of isocyanate groups reached 3.67%.

[0417] Next, the reaction solution was cooled to 80°C, and 9.90 g of N-methyldiethanolamine, a cationic active hydrogen compound, was added. The reaction was carried out at 80°C for 1 hour.

[0418] Next, 50.00 g of methyl ethyl ketone was added as a solvent, and the reaction was carried out at 80 °C until the isocyanate groups were confirmed to have disappeared by infrared absorption spectroscopy.

[0419] Next, 57.69g of methyl ethyl ketone was added to the reaction solution, the temperature was raised to 80°C, and the mixture was stirred until the reaction solution was completely dissolved. Then, the mixture was cooled to 75°C.

[0420] Then, 18.96g of acetic acid, an acid compound, was added for neutralization.

[0421] Next, while keeping the reaction solution at 75°C, slowly add 800.0g of ion-exchange water heated to 70°C to emulsify it (internal emulsification).

[0422] Next, solvent removal is carried out using an evaporator at a water bath temperature of 60°C under reduced pressure until the concentration of solid components reaches more than 20% by weight.

[0423] Next, the concentration of solid components other than acidic compounds (acetic acid) was adjusted to 20% by weight using ion-exchanged water, resulting in an aqueous dispersion containing polyurethane.

[0424] Manufacturing Example 10 In a 500 mL four-necked flask equipped with a stir bar, thermometer, and reflux tube, 116 g of sorbitol tristearate and 150 g of 4-methyl-2-pentanone (MIBK) were added. Next, to remove excess water vapor from the mixture, it was stirred while maintaining the temperature at 70°C and refluxed for 1 hour, then cooled to 50°C. Then, while maintaining stirring, 30 g of Desmodur N-100 (a biuret derivative of hexamethylene diisocyanate, manufactured by Covestro) was added dropwise using a dropping funnel. After the addition was complete, one drop of dibutyltin dilaurate was added as a catalyst, and the reaction was carried out at 80°C for 1 hour. Then, 25 g of sorbitol monostearate was added, and the reaction was carried out at 80°C for another 4 hours.

[0425] Next, after cooling to 60°C, the reaction solution was recovered, and the reaction solution was slowly mixed with water at 60°C containing any amount of cationic emulsifier and polyoxyethylene alkyl ether. The mixture was stirred at 6000 rpm for 1 minute using a homogenizer, and then ultrasonically emulsified and dispersed for 15 minutes. Then, the solvent (MIBK) was removed by vacuum, and pure water was added to adjust the concentration to obtain an aqueous dispersion of polyurethane containing 20% ​​solid components.

[0426] Manufacturing Example 11 150 g of methyl ethyl ketone (MEK) and 51 g of stearyl alcohol were added to a 500 mL four-necked flask equipped with a stir bar, thermometer, and reflux tube. Next, to remove excess water vapor from the mixture, it was stirred while maintaining the temperature at 70 °C and refluxed for 1 hour, then cooled to 50 °C. Then, 30 g of Desmodur N3200A (a biuret derivative of hexamethylene diisocyanate, manufactured by Covestro) was added, and the mixture was reacted at 80 °C for 4 hours.

[0427] Next, after cooling to 60°C, the reaction solution was recovered, and the reaction solution was slowly mixed with water at 60°C containing any amount of polyoxyethylene alkyl ether. The mixture was stirred at 6000 rpm for 1 minute using a homogenizer, and then ultrasonically emulsified and dispersed for 15 minutes.

[0428] Then, after removing the solvent (MEK) by vacuum decompression, pure water was added to adjust the concentration, resulting in an aqueous dispersion of polyurethane containing 20% ​​solid components.

[0429] (Example of manufacturing an aqueous dispersion containing organosilicon) Manufacturing Example 12 12 g of methyl hydrogen-containing organosilicon oil (SiH:SiCH3 molar ratio of 50:50 as determined by 1H NMR) and 0.02 g of platinum catalyst were added to a 200 mL four-necked flask equipped with a stir bar, thermometer, and reflux tube. Next, 36 g of 1-hexadecene was added dropwise through a 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 organosilicon polymer.

[0430] Next, 28g of organosilicon polymer, 5.6g of water-soluble glycol solvent, 60g of purified water, 1.7g of dehydrated sorbitan fatty acid ester, 0.7g of polyoxyethylene alkyl ether, and 0.6g of cationic emulsifier were added to a 250ml glass container. The mixture was heated to 75℃, stirred at 2000rpm for 1 minute using a homogenizer, and then ultrasonically emulsified and dispersed for 10 minutes to obtain an aqueous dispersion of the organosilicon polymer. Then, purified water was added to prepare an aqueous dispersion of the organosilicon polymer with a solid component concentration of 30% by weight.

[0431] (Example of manufacturing a wax-containing aqueous dispersion) Manufacturing Example 13 150g of paraffin wax (melting point 75℃), 350g of pure water, 4.5g of polyoxyethylene alkyl ether, and 3g of dehydrated sorbitan fatty acid ester were added to a pressure reaction vessel and sealed. The mixture was heated to 110–120℃ under stirring and then subjected to high-pressure emulsification for 30 minutes to prepare an aqueous dispersion of the wax. Then, pure water was added to prepare an aqueous dispersion of wax with a solid content of 30% by weight.

[0432] Manufacturing Example 14 150g of oxidized polypropylene wax (melting point 150℃, acid value 44mgKOH / g, density 0.93), 325g of deionized water, 25g of HLB15 surfactant, and 5g of 48% potassium hydroxide aqueous solution were added to a reaction vessel and sealed. The mixture was heated to 160℃ with stirring, and then subjected to high-pressure emulsification for 1 hour. After cooling to 90℃, an aqueous dispersion of polypropylene wax was obtained. Then, pure water was added to prepare an aqueous dispersion of polypropylene wax with a solid content of 30% by weight.

[0433] [Examples 1-13, Comparative Examples 1-3] Add the above-mentioned aqueous dispersion and the hydrophilic particles shown in Table 2 (average primary particle size 25 nm, Zeta potential +45 mV, turbidity 2.0 ppm) and mix to obtain an aqueous dispersion with a solid component concentration of 30% that matches the composition weight ratio shown in Table 2. Dilute the aqueous dispersion with tap water to prepare 1000 g of test solution with a solid component concentration of 1.0% by weight. Next, immerse the test fabric (polyester or nylon fabric) in the test solution, then pass it through a fabric rolling mill. The test fabric is then passed through a needle tenter frame at 160°C for 1 minute for drying and curing, and then the above test is performed.

[0434] [Example 14] Add the above-mentioned aqueous dispersion and the antibacterial and antifungal agents shown in Table 2 (75 ppm of benzisothiazolin-3-one and 75 ppm of a mixture of 5-chloro-2-methyl-2H-isothiazolin-3-one and 2-methyl-2H-isothiazolin-3-one (weight ratio 3:1)) and mix to obtain an aqueous dispersion with a solid component concentration of 30% matching the weight ratio of the composition shown in Table 2. Dilute the aqueous dispersion with tap water to prepare 1000 g of test solution with a solid component concentration of 1.0% by weight. Then, immerse the test fabric (polyester fabric or nylon fabric) in the test solution, pass it through a fabric rolling mill, and then pass it through a needle tenter frame at 160°C for 1 minute for drying and curing, and then conduct the above-mentioned test.

[0435] [Table 2] The implementation methods have been described above, but it should be understood that various changes can be made to the methods and details as long as they do not depart from the spirit and scope of the claimed protection.

Claims

1. A water-repellent composition, characterized in that, contain: A nonfluorinated copolymer (A) comprising repeating units derived from a hydrophobic monomer (a1) and repeating units derived from a chloride monomer (a2), wherein the monomer (a1) has a hydrocarbon group having 2 to 40 carbon atoms, and the monomer (a2) is at least one selected from vinyl chloride and vinylidene chloride; and Isocyanate derivatives (B). In the non-fluorinated copolymer (A), the amount of repeating units derived from monomer (a2) is 1 to 15 by weight, relative to the total amount of repeating units derived from monomer (a1) and repeating units derived from monomer (a2).

2. The water-repellent composition according to claim 1, characterized in that, The hydrocarbon group in the hydrophobic monomer (a1) is a straight-chain alkyl group with 10 or more carbon atoms.

3. The water-repellent composition according to claim 1 or 2, characterized in that, The hydrophobic monomer (a1) has the formula: CH2=C(-R 12 ) - C (= O) - Y 11 - (R) 11 ) k The compound shown, In the formula, R 11 It consists of hydrocarbon groups with 2 to 40 carbon atoms. R 12 It can be a hydrogen atom, a monovalent organic group, or a halogen atom. Y 11 The valence bond is a hydrocarbon group with 1 carbon atom in the 2- to 4-valent group, consisting of at least one group selected from -C6H4-, -O-, -C(=O)-, -S(=O)2-, and -NR'-, wherein R' is a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms. k ranges from 1 to 3.

4. The water-repellent composition according to any one of claims 1 to 3, characterized in that, The isocyanate derivative (B) has an alkyl group having 12 to 30 carbon atoms.

5. The water-repellent composition according to any one of claims 1 to 4, characterized in that, The isocyanate derivative (B) is polyurethane.

6. The water-repellent composition according to any one of claims 1 to 5, characterized in that, The isocyanate derivative (B) is a compound obtained by reacting an active hydrogen compound with a raw isocyanate. The active hydrogen compound is selected from at least one of hydrocarbon alcohols, sugar alcohol modifiers and hydroxy acid modifiers, and the raw material isocyanate is selected from at least one of noncyclic aliphatic polyisocyanates and their derivatives.

7. The water-repellent composition according to any one of claims 1 to 6, characterized in that, It contains organosilicon.

8. The water-repellent composition according to claim 7, characterized in that, The amount of organosilicon is 0.1 to 20 parts by weight relative to 100 parts by weight of the non-fluorinated copolymer (A).

9. The water-repellent composition according to any one of claims 1 to 8, characterized in that, In the non-fluorinated copolymer (A), the amount of repeating units derived from monomer (a2) is 1 to 9 by weight, relative to the total amount of repeating units derived from monomer (a1) and repeating units derived from monomer (a2).

10. The water-repellent composition according to any one of claims 1 to 9, characterized in that, The amount of the isocyanate derivative (B) is 0.1 to 20 parts by weight relative to 100 parts by weight of the non-fluorinated copolymer (A).

11. The water-repellent composition according to claim 1, characterized in that, The hydrophobic monomer (a1) has the formula: CH2=C(-R 12 ) - C (= O) - Y 11 - (R) 11 ) k The compound shown, In the formula, R 11 It consists of hydrocarbon groups with 2 to 40 carbon atoms. R 12 It can be a hydrogen atom, a monovalent organic group, or a halogen atom. Y 11 The valence bond is a hydrocarbon group with 1 carbon atom in the 2- to 4-valent group, consisting of at least one group selected from -C6H4-, -O-, -C(=O)-, -S(=O)2-, and -NR'-, wherein R' is a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms. k is 1 to 3 The isocyanate derivative (B) is an alkyl group having 12 to 30 carbon atoms, obtained by reacting an active hydrogen compound with a starting isocyanate. The active hydrogen compound is selected from at least one of hydrocarbon alcohols, sugar alcohol modifiers, and hydroxy acid modifiers, and the raw isocyanate is selected from at least one of acyclic aliphatic polyisocyanates and their derivatives. The amount of the isocyanate derivative (B) is 0.1 to 20 parts by weight relative to 100 parts by weight of the non-fluorinated copolymer (A).

12. The water-repellent composition according to claim 1, characterized in that, The hydrophobic monomer (a1) has the formula: CH2=CH-C(=O)-Y 11 -R 11 The compound shown, In the formula, R 11 Alkyl groups having 12 to 25 carbon atoms Y 11 It is -O- or -O- (CH2). m -NH-C(=O)-, m is an integer of 2 or 4. The chloride monomer (a2) is vinyl chloride. The isocyanate derivative (B) is a compound obtained by reacting a hydrocarbon alcohol having 12 to 25 carbon atoms with an isocyanurate derivative of an acyclic aliphatic polyisocyanate having 2 to 10 carbon atoms, or a compound obtained by reacting an alkyl-modified anhydrous sorbitol derivative having 12 to 25 carbon atoms with a biuret derivative of an acyclic aliphatic polyisocyanate having 2 to 10 carbon atoms. The amount of the isocyanate derivative (B) is 1 to 10 parts by weight relative to 100 parts by weight of the non-fluorinated copolymer (A).

13. A method for manufacturing a fiber product, characterized in that, The step includes applying the water-repellent composition of any one of claims 1 to 12 to a fiber substrate.

14. The method for manufacturing a fiber product as described in claim 13, characterized in that, include: The process of imparting functional groups to the fibers prior to applying the water-repellent composition to the fiber substrate. Wherein, the functional group is selected from -SO3M 1 The monovalent group shown, -COOM 2 The monovalent groups shown and -O-P(O)(OX) 1 (OX) 2 One or more of the monovalent groups shown in the formula, where M 1 M represents a monovalent cation. 2 X represents a monovalent cation. 1 and X 2 Alkyl groups, which can be independently represented by 1 to 22 hydrogen atoms or carbon atoms respectively.

15. A fiber product, characterized in that, The non-fluorinated copolymer (A) and the isocyanate derivative (B) of any one of claims 1 to 12 are attached to the water-repellent composition.

16. The fiber article as described in claim 15, characterized in that, Attached with a substance selected from SO3M 1 The monovalent group shown, -COOM 2 The monovalent groups shown and -O-P(O)(OX) 1 (OX) 2 A compound having one or more functional groups in a monovalent group as shown in the formula, where M 1 M represents a monovalent cation. 2 X represents a monovalent cation. 1 and X 2 Alkyl groups, which can be independently represented by 1 to 22 hydrogen atoms or carbon atoms respectively.

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