Water repellent composition

Abstract

The present disclosure provides a water repellent composition containing a non-fluorine copolymer (A) containing: a repeating unit derived from a hydrophobic monomer (a1) having a hydrocarbon group having 2-40 carbon atoms; and a repeating unit derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride, wherein, in the non-fluorine copolymer (A), the amount of the repeating unit derived from the monomer (a2) is 1-9 wt% with respect 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).

Description

Water repellent composition

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

[0002] Non-fluorine-based water repellents have been developed as water repellents for imparting water repellency to substrates (particularly textile products).

[0003] International Publication No. 2021 / 132172 Japanese Patent Application Laid-Open No. 2020-189980

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

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

[0006] The present disclosure includes the following aspects: [Item 1] A water repellent composition comprising a fluorine-free copolymer (A) comprising repeating units derived from a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms, and repeating units derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride, wherein in the fluorine-free copolymer (A), the amount of repeating units derived from the monomer (a2) is 1 to 9 wt % based on the total amount of repeating units derived from the monomer (a1) and the amount of repeating units derived from the monomer (a2). [Item 2] The water repellent 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. [Item 3] The hydrophobic monomer (a1) is a group represented by the formula: CH ２ =C(-R １２ )-C(=O)-Y １１ - (R １１ ) ｋ [In the formula, R １１ is a hydrocarbon group having 2 to 40 carbon atoms, R １２ is a hydrogen atom, a monovalent organic group or a halogen atom, １１ represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２- and -NR'- (R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), and k is 1 to 3.] [Item 4] The water repellent composition according to any one of Items 1 to 3, which contains a silicone. [Item 5] The water repellent composition according to Item 4, wherein the amount of the silicone is 0.1 to 10 parts by mass per 100 parts by mass of the non-fluorinated copolymer (A). [Item 6] The water repellent composition according to any one of Items 1 to 5, wherein in the non-fluorinated copolymer (A), the amount of repeating units derived from the monomer (a2) is 3 to 7 wt % relative to the total amount of repeating units derived from the monomer (a1) and the amount of repeating units derived from the monomer (a2). [Item 7] The water repellent composition according to any one of Items 1 to 6, which further contains an isocyanate derivative (B). [Item 8] The water repellent composition according to Item 7, wherein the isocyanate derivative (B) has an alkyl group having from 12 to 30 carbon atoms. [Item 9] The water repellent composition according to Item 7 or 8, wherein the isocyanate derivative (B) is polyurethane. [Item 10] The water repellent composition according to any one of Items 7 to 9, wherein the amount of the isocyanate derivative (B) is 0.1 to 10 parts by mass per 100 parts by mass of the non-fluorinated copolymer (A). [Item 11] The water repellent composition according to Items 7 to 10, wherein the isocyanate derivative (B) is a compound obtained by reacting at least one active hydrogen compound selected from the group consisting of hydrocarbon alcohols, sugar alcohol-modified compounds, and hydroxy acid-modified compounds with at least one raw material isocyanate selected from the group consisting of acyclic aliphatic polyisocyanates and derivatives thereof. [Item 12] The hydrophobic monomer (a1) is a compound represented by the formula: CH ２ =C(-R １２ )-C(=O)-Y １１ - (R １１ ) ｋ [In the formula, R １１ is a hydrocarbon group having 2 to 40 carbon atoms, R １２ is a hydrogen atom, a monovalent organic group or a halogen atom, １１ represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H４ -, -O-, -C(=O)-, -S(=O) ２ - and -NR'- (R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), and k is 1 to 3.], and the amount of repeating units derived from the monomer (a2) in the fluorine-free copolymer (A) is 3 to 7 wt % based on the total amount of repeating units derived from the monomer (a1) and the amount of repeating units derived from the monomer (a2). [Item 13] The water repellent composition according to Item 1, wherein the hydrophobic monomer (a1) is a compound represented by the formula: CH ２ =CH-C(=O)-Y １１ -R １１ [In the formula, R １１ is an alkyl group having 12 to 25 carbon atoms; Y １１ is -O- or -O-(CH ２ ) m Item 14. A water repellent composition according to Item 1, wherein the chloride monomer (a2) is vinyl chloride, and the amount of repeating units derived from the monomer (a2) in the non-fluorinated copolymer (A) is 3 to 7 wt % based on the total amount of repeating units derived from the monomer (a1) and the amount of repeating units derived from the monomer (a2). [Item 15] A method for producing a textile product, comprising applying the water repellent composition according to any one of Items 1 to 13 to a textile substrate. [Item 16] A method for producing a textile product, comprising applying a water repellent composition according to any one of Items 1 to 13 to a textile substrate. [Item 17] A method for producing a textile product, comprising applying a water repellent composition according to any one of Items 1 to 15 to a textile substrate. [Item 18] A method for producing a textile product, comprising applying a water repellent composition according to any one of Items 1 to 15 to a textile substrate. [Item 19] A method for producing a textile product, comprising applying a water repellent composition according to any one of Items 1 to 16 to a textile substrate. ３ M １ (In the formula, M １ represents a monovalent cation), ２ (In the formula, M ２ represents a monovalent cation), and １ ) (OX ２ ) (wherein, X １ and X ２[Item 16] A method for producing a textile product according to Item 14, comprising a step of providing one or more functional groups selected from the group consisting of monovalent groups represented by the formula: ３ M １ (In the formula, M １ represents a monovalent cation), ２ (In the formula, M ２ represents a monovalent cation), and １ ) (OX ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.

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

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

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

[0010] In this specification, when a term (symbol) that may appear multiple times in a chemical structure is defined, that definition applies independently at each occurrence, unless otherwise stated, regardless of whether "independently at each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated.

[0011] The chemical structures described herein should be understood not to encompass chemical structures that would be recognized by those skilled in the art as chemically impossible or extremely unstable.

[0012] <Water Repellent Composition> The water repellent composition according to the present disclosure comprises a fluorine-free copolymer (A) containing repeating units derived from a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms, and repeating units derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride. In the fluorine-free copolymer (A), the amount of repeating units derived from the monomer (a2) is 1 to 9 wt % based on the total amount of repeating units derived from the monomer (a1) and the repeating units derived from the monomer (a2). The water repellent composition according to the present disclosure is capable of adhering to a substrate (particularly a textile product) and imparting both good water repellency and good slip resistance to the substrate.

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

[0014] [(A) Fluorine-free copolymer] The fluorine-free copolymer (A) does not contain fluorine atoms.

[0015] The fluorine-free copolymer (A) contains repeating units derived from a hydrophobic monomer (a1), and repeating units derived from a chloride monomer (a2). The fluorine-free copolymer (A) may further contain a cyclic hydrocarbon group-containing monomer (a3) ​​and / or a crosslinkable monomer (a4). The fluorine-free copolymer (A) may contain another monomer (a5).

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

[0017] The hydrophobic monomer (a1) may have at least one hydrocarbon group having 2 to 40 carbon atoms. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The hydrocarbon group may be linear or branched, and is preferably linear. The number of carbon atoms in the hydrocarbon group may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 11 or more, 12 or more, 14 or more, or 16 or more, and preferably 6 or more. The number of carbon atoms in the hydrocarbon group may be 40 or less, 30 or less, 25 or less, 22 or less, or 20 or less, and preferably 30 or less.

[0018] The hydrophobic monomer (a1) has the formula: CH ２ =C(-R １２ )-C(=O)-Y １１ - (R １１ ) ｋ [In the formula, R １１ is a hydrocarbon group having 2 to 40 carbon atoms, R １２ is a hydrogen atom, a monovalent organic group or a halogen atom, １１ represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - and -NR'- (R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), and k is an integer of 1 to 3.

[0019] R １１is preferably a branched or linear (preferably long linear) hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. ３ The group is -CH ２ - has a lower surface free energy than - and is more likely to exhibit liquid repellency. ３ A structure with many groups is preferred. On the other hand, long-chain alkyl groups of a certain length exhibit high liquid repellency due to their crystallinity. Therefore, branched hydrocarbon groups (for example, branched alkyl groups), particularly t-butyl groups and isopropyl groups, groups with multi-branched structures, or long-chain hydrocarbon groups (or long-chain linear hydrocarbon groups), for example, alkyl groups, may be used. R １１ The number of carbon atoms in R may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 11 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and is preferably 10 or more. １１ may have 40 or fewer, 30 or fewer, 25 or fewer, 20 or fewer, 15 or fewer, or 12 or fewer carbon atoms.

[0020] k is 1, 2 or 3. １１ has a tetravalent hydrocarbon group having one carbon atom, k=3. １１ has a trivalent hydrocarbon group having one carbon atom, k=2. １１ does not have a trivalent or tetravalent hydrocarbon group having one carbon atom (for example, Y １１ is a divalent hydrocarbon group having one carbon atom (-CH ２ -), k=1.

[0021] R １２ R may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. １２ Examples of R are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. １２ is preferably a hydrogen atom, a methyl group, or a chlorine atom. １２ More preferably, R is a methyl group. １２ When R is a methyl group, higher liquid repellency can be obtained. １２may be a hydrogen atom, particularly from the viewpoint of reactivity.

[0022] Y １１ is preferably a divalent group. Examples of divalent to tetravalent hydrocarbon groups having one carbon atom include -CH ２ -, a branched -CH=, and a branched -C≡.

[0023] Y １１ represents -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'- (wherein each Y' independently represents a direct bond, -O-, -NR'- (R' represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), or -S(=O) ２ - and X' is -(CH ２ ) ｍ - (m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH ２ ) ｌ -C ６ H ４ -(CH ２ ) ｌ -(each l is independently an integer of 0 to 5, -C ６ H ４ - is a phenylene group). １１ is preferably not exclusively a divalent hydrocarbon group.

[0024] Y １１ Specific examples are -O-, -NH-, -OC(=O)-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C ６ H ４ -, -NH-C ６ H ４ -, -O-(CH ２ ) m -O-, -NH-(CH ２ ) m -NH-, -O-(CH ２ )m -NH-、-NH-(CH ２ ) m -O-、-O-(CH ２ ) m -O-C(=O)-、-O-(CH ２ ) m -C(=O)-O-,-NH-(CH ２ ) m -O-C(=O)-,-NH-(CH ２ ) m -C(=O)-O-、-O-(CH ２ ) m -O-C(=O)-NH-,-O-(CH ２ ) m -NH-C(=O)-O-,-O-(CH ２ ) m -C(=O)-NH-,-O-(CH ２ ) m -NH-C(=O)-,-O-(CH ２ ) m -NH-C(=O)-NH-,-O-(CH ２ ) m -O-C ６ H ４ -、-O-(CH ２ ) m -NH-S(=O) ２ -、-O-(CH ２ ) m -S(=O) ２ -NH-、-NH-(CH ２ ) m -NH-S(=O) ２ -、-NH-(CH ２ ) m -S(=O) ２ -NH--NH-(CH ２ ) m -O-C(=O)-NH-,-NH-(CH ２ ) m -NH-C(=O)-O-,-NH-(CH ２ ) m -C(=O)-NH-,-NH-(CH ２ ) m -NH-C(=O)-,-NH-(CH ２ ) m -NH-C(=O)-NH-,-NH-(CH ２) m -O-C ６ H ４ -, or -NH-(CH ２ ) m -NH-C ６ H ４ wherein m is an integer from 1 to 5, particularly 2 or 4.

[0025] Y １１ is -O-, -NH-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -NH-S(=O) ２ - or -O-(CH ２ ) m -S(=O) ２ -NH-, -NH-(CH ２ ) m -OC(=O)-, -NH-(CH ２ ) m -NH-C(=O)-, -NH-(CH ２ ) m -OC(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-O-, -NH-(CH ２ ) m -NH-C(=O)-NH- [wherein m is an integer of 1 to 5, particularly 2 or 4] is preferred. １１ is -O-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, or -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m-NH-S(=O) ２ - or -O-(CH ２ ) m -S(=O) ２ -NH-, especially -O-(CH ２ ) m It is more preferably —NH—C(═O)—.

[0026] Y １１ is -O-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, or -O-(CH ２ ) m More preferably, it is —NH—C(═O)—, where m is an integer of 1 to 5, particularly 2 or 4.

[0027] Y １１ is -O- or -O-(CH ２ ) ２ It is particularly preferably —NH—C(═O)—.

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

[0029] The hydrophobic monomer (a1) may have a water solubility at 25°C of 10 g / L or less, 5 g / L or less, 3 g / L or less, 1 g / L or less, 0.5 g / L or less, or 0.1 g / L or less, preferably 3 g / L or less. The homopolymer of the hydrophobic monomer (a1) may have a water solubility at 25°C of 10 g / L or less, 5 g / L or less, 3 g / L or less, 1 g / L or less, 0.5 g / L or less, or 0.1 g / L or less, preferably 3 g / L or less.

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

[0031] Specific examples of the hydrophobic monomer (a1) are as follows: The compound of the following chemical formula is an acrylic compound having a hydrogen atom at the α-position, but may also be a methacrylic compound having a methyl group at the α-position or an α-chloroacrylic compound having a chlorine atom at the α-position. CH ２ =CHC(=O)OC １８ H ３７ CH ２ =CHC(=O)OC ｎ H ２ｎ＋１ CH ２ =CHC(=O)OC ２ H ４ OC(=O)NHC １８ H ３７ CH ２ =CHC(=O)OC ２ H ４ NHC(=O)OC １８ H ３７ CH ２ =CHC(=O)OC ｍ H ２ｍ NHC(=O)C ｎ H ２ｎ＋１ CH ２ =CHC(=O)OC ２ H ４ OC(=O)NHC ｎ H ２ｎ＋１ CH ２ =CHC(=O)OC ２ H ４NHC(=O)OC ｎ H ２ｎ＋１ CH ２ =CHC(=O)OC ２ H ４ NHC(=O)NHC ｎ H ２ｎ＋１ CH ２ =CHC(=O)OC ４ H ８ OC(=O)NHC ｎ H ２ｎ＋１ CH ２ =CHC(=O)NHC ｍ H ２ｍ OC(=O)NHC ｎ H ２ｎ＋１ CH ２ =CHC(=O)OC ｍ H ２ｍ NHSO ２ C ｎ H ２ｎ＋１ CH ２ =CHC(=O)OC ｍ H ２ｍ SO ２ NHC 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.]

[0032] Preferred specific examples of the hydrophobic monomer (a1) include stearyl (meth)acrylate, butyl (meth)acrylate, t-butyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, icosyl α-chloroacrylate, behenyl α-chloroacrylate, stearamidoethyl (meth)acrylate, 2-stearamidoethyl acrylate, CH ２ =CHC(=O)OC ２ H ４ NHSO ２ C １８ H ３７These may be used alone or in combination of two or more.

[0033] From the viewpoint of liquid repellency, the hydrophobic monomer (a1) may contain a hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group. A combination of a hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group with a hydrophobic monomer (a1) not having an amide group, a urea group, or a urethane group may also be used. Examples of the hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group include a hydrophobic monomer (a1) having a CH═C(-R １２ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R １１ , C.H. ２ =C(-R １２ )-C(=O)-O-(CH ２ ) ｍ -OC(=O)-NH-R １１ , C.H. ２ =C(-R １２ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-OR １１ , and C.H. ２ =C(-R １２ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-NH-R １１ The hydrophobic monomer (a1) is CH═C(-R １２ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R １１ may include:

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

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

[0036] The cyclic hydrocarbon group-containing monomer (a3) ​​preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0037] The cyclic hydrocarbon group may be aliphatic or aromatic, preferably aliphatic. The cyclic hydrocarbon group may be saturated or unsaturated, preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, preferably a bridged ring group. The cyclic hydrocarbon group may have a chain group (e.g., a linear or branched chain hydrocarbon group).

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

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

[0040] Specific examples of the cyclic hydrocarbon group-containing monomer (a3) ​​include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and compounds in which these acrylates are substituted with acrylamide, etc. These may be used alone or in combination of two or more.

[0041] ((a4) Crosslinkable Monomer) The fluorine-free copolymer (A) may have a repeating unit derived from a crosslinkable monomer (a4). The crosslinkable monomer (a4) is a monomer capable of imparting crosslinkability to the copolymer, and may have at least two groups selected from the group consisting of reactive groups and olefinic carbon-carbon double bonds. The crosslinkable monomer (a4) may be a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group.

[0042] The crosslinkable monomer (a4) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0043] Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, a carbonyl group, an isocyanate group (blocked isocyanate group), and the like.

[0044] Specific examples of the crosslinkable monomer (a4) include diacetone (meth)acrylamide, N-methylol (meth)acrylamide, hydroxyethyl (meth)acrylamide, glycidyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and compounds in which these acrylates are substituted with acrylamide. These may be used alone or in combination of two or more. These may be used alone or in combination of two or more.

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

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

[0047] (Polymer Composition) The amount of repeating units derived from the hydrophobic monomer (a1) may be 50% by weight or more, 60% by weight or more, 65% by weight or more, 70% by weight or more, 75% by weight, 80% by weight or more, or 85% by weight or more, relative to the fluorine-free copolymer (A). The amount of repeating units derived from the hydrophobic monomer (a1) may be 99% by weight or less, 98% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less, relative to the fluorine-free copolymer (A).

[0048] Among the repeating units derived from the hydrophobic monomer (a1), the ratio of the hydrophobic monomer (a1) having an amide group, urea group, or urethane group may be 1 wt% or more, 3 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, 50 wt% or more, or 75 wt% or more. Among the repeating units derived from the hydrophobic monomer (a1), the ratio of the hydrophobic monomer (a1) having an amide group, urea group, or urethane group may be 100 wt% or less, 90 wt% or less, 80 wt% or less, or 70 wt% or less.

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

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

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

[0052] The amount of repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, relative to the fluorine-free copolymer (A). The amount of repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​may be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, or 5% by weight or less, relative to the fluorine-free copolymer (A).

[0053] The amount of the repeating units derived from the crosslinkable monomer (a4) may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, relative to the fluorine-free copolymer (A). The amount of the repeating units derived from the crosslinkable monomer (a4) may be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, or 5% by weight or less, relative to the fluorine-free copolymer (A).

[0054] The amount of repeating units derived from the other monomer (a5) may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, relative to the fluorine-free copolymer (A). The amount of repeating units derived from the other monomer (a5) may be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less, relative to the fluorine-free copolymer (A).

[0055] The amount of the repeating units derived from the chloride monomer (a2) may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 25 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1). The amount of the repeating units derived from the chloride monomer (a2) may be 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, or 6 parts by weight or less, relative to 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1).

[0056] The amount of the repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​may be 2.5 parts by weight or more, 5 parts by weight or more, 12.5 parts by weight or more, 25 parts by weight or more, 35 parts by weight or more, or 45 parts by weight or more, relative to 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1). The amount of the repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​may be 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1).

[0057] The amount of the repeating units derived from the crosslinkable monomer (a4) may be 2.5 parts by weight or more, 5 parts by weight or more, 12.5 parts by weight or more, 25 parts by weight or more, 35 parts by weight or more, or 45 parts by weight or more, relative to 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1). The amount of the repeating units derived from the crosslinkable monomer (a4) may be 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1).

[0058] The amount of the repeating units derived from the other monomer (a5) may be 2.5 parts by weight or more, 5 parts by weight or more, 12.5 parts by weight or more, 25 parts by weight or more, 35 parts by weight or more, or 45 parts by weight or more, relative to 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1). The amount of the repeating units derived from the other monomer (a5) may be 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1).

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

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

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

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

[0063] The weight average molecular weight of the isocyanate derivative (B) may be 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more. The weight average molecular weight of the isocyanate derivative (B) may be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, or 5,000 or less.

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

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

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

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

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

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

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

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

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

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

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

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

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

[0077] In one embodiment, R α２may contain at least one unsaturated bond. Examples of such compounds (wherein at least one active hydrogen substituent is —C(O)R α２ and R α２ contains at least one unsaturated bond), sorbitan trioleate (i.e., in which R α２ Ha-C7H 14 CH=CHC8H 17 Other examples include, but are not limited to, mono-, di-, and tri-substituted sorbitans derived from palmitoleic acid, linoleic acid, arachidonic acid, and erucic acid.

[0078] In one embodiment, the sorbitan modification (α21) has at least one active hydrogen substituent, and the active hydrogen substituent is independently —(CHCHO). n (CH(CH3)CH2O) m R α２ or -(CHCHO) n (CH(CH3)CH2O) m C(O)R α２ (wherein each m is independently 0 to 20, each n is independently 0 to 20, and m+n is greater than 0.) Such compounds are known as polysorbates and are commercially available under the trade name TWEEN. These sorbitans are also known as R α２ Commercially available polysorbates can be mono-, di-, or trisubstituted with each R 2 From various polysorbates where R is H (unsubstituted), α２ It is known that sorbitan derivatives contain a wide variety of mixtures ranging from polysorbates in which m is a linear or branched alkyl group having 6 to 40 carbons (fully substituted), and mixtures of these various substitutions. Examples of such sorbitan modifications (α21) include polysorbates such as polysorbate tristearate and polysorbate monostearate. m+n is greater than 0 and R α２ Examples of sorbitan modifications (α21) containing at least one unsaturated bond include, but are not limited to, polysorbate trioleate (where R α２is C7H 14 CH=CHC8H 17 and is commercially available under the name Polysorbate 80. Sorbitan modifications (α21) may include mixtures of compounds with various active hydrogen substituents, and R α２ a compound in which R α２ may include mixtures with fully saturated compounds.

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

[0080] ((α23) Pentaerythritol Modification) The sugar alcohol / hydroxy acid modification (α21) may be a pentaerythritol modification (α23) in which pentaerythritol is modified with a hydrocarbon group having from 6 to 40 carbon atoms, and may be a mono-, di-, or tri-substituted product having a hydrocarbon group (particularly an alkyl group) having from 6 to 40 carbon atoms, such as a dipentaerythriol ester. The active hydrogen substituent is —CHC[CHOR α２ ]3, where R α２ is a hydrocarbon group having 6 to 40 carbon atoms.) The pentaerythritol modification (α23) is a compound having a mixture of hydrocarbon groups with different chain lengths, or R α２ a compound in which R α２ The pentaerythritol modified product (α23) may contain a mixture of a compound having 6 to 40 carbon atoms and a compound having 12 to 30 carbon atoms. The hydrocarbon group in the pentaerythritol modified product (α23) may be the hydrocarbon group having 6 to 40 carbon atoms as described above, and the above explanation is incorporated herein by reference. The pentaerythritol modified product (α23) may have an alkyl group having 12 to 30 carbon atoms. The above explanation is incorporated herein by reference for the alkyl group having 12 to 30 carbon atoms.

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

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

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

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

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

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

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

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

[0089] Examples of the acid compound include organic acids and inorganic acids. Examples of the organic acid include acetic acid, lactic acid, tartaric acid, malic acid, etc., preferably acetic acid and lactic acid, more preferably acetic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, etc., preferably hydrochloric acid. Examples of the acid compound include organic acids. When the acid compound contains an organic acid, the acid volatilizes upon heat treatment, thereby improving the water repellency of the water-repellent treated material treated with this water repellent composition. Furthermore, the acid volatilizes upon heat treatment, which makes it easier for cationic groups to adsorb to textile products, thereby improving the washing durability of the textile products. [(α4) Other Active Hydrogen-Containing Compounds] The active hydrogen compound (α) may contain other active hydrogen compounds (α4).

[0090] ((α41) Compound) The active hydrogen compound (α4) is represented by the formula R α４１ -X α４１ [In the formula, In the formula, R α４１ is a C1-C2 alkyl group which may contain at least one unsaturated group; 30 Straight or branched chain alkyl, hydroxy-functional C1-C 30Straight or branched chain alkyl, hydroxy-functional straight or branched chain C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy-functional linear or branched organosiloxanes, thiol-functional C1-C 30 Straight or branched alkyl, amine functional C1-C 30 linear or branched alkyl, Y － R α４１１ R α４１２ R α４１３ N ＋ -R α４１４ - (where Y is a halide ion, e.g., Cl － ), HOS(=O) ２ -R α４１４ - or R α４１１ R α４１２ C=N- (where R α４１１ , R α４１２ , R α４１３ are each independently —H or C1-C6 alkyl, and R α４１４ is a divalent alkyl group having 1 to 20 carbon atoms; α４１ is -OH, -C(O)OH, -SH, -NH(R'), -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CHCHO) s (CH(CH3)CH2O) t isocyanate-reactive functional groups such as —H, where R ’ represents —H or a monovalent organic group, s represents an integer of 0 to 50, t represents an integer of 0 to 50, and s+t is greater than 0.

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

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

[0093] X α４１ may be —OH, and examples of such compounds (α41) include alkyl alcohols such as propanol, butanol, or fatty alcohols including stearyl alcohol (R α４１ optionally containing at least one unsaturated group, C1-C 30 alkyl diols or polyols (R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 4 α４１ is a hydroxy-functional C-C 30 alkylene glycol ethers such as triethylene glycol, tetraethylene glycol, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), or glycol ethers (R ) having a mixture of PEG, PPG or THF units;α４１ is a hydroxy-functional straight or branched chain C-C 30 Polyether), polyester polyol (R α４１ is a hydroxy-functional linear or branched polyester), silicone prepolymer polyol (R α４１ is a hydroxy-functional linear or branched organosiloxane), N,N-dimethylaminoethanol (R α４１ is an amine functional C-C 30 straight or branched chain alkyl), choline chloride or betaine HCl (R α４１ Is Y － R α４１１ R α４１２ R α４１３ N ＋ -R α４１４ -), butanone oxime (R α４１ is R α４１１ R α４１２ Polyether polyols include, but are not limited to, polyether glycols (wherein the hydroxyl group is C═N—). The polyether polyols can contain only EO groups, only PO groups, only THF groups, or mixtures thereof. These polyethers can also exist as block copolymers, such as those designated by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). The polyether glycols preferably have an average molecular weight of about 200 or greater, most preferably 350 to 2000.

[0094] X α４１ may be —C(O)OH, and examples of such compounds (α41) include fatty acids (R α41) such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, linoleic acid, arachidonic acid, oleic acid, or erucic acid. α４１ is a C-C group optionally containing at least one unsaturated group 30hydroxy-containing acids (R alkyl esters), such as hydroxycaprylic acid, hydroxycapric acid, hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyarachidic acid, hydroxybehenic acid, hydroxylignoceric acid, hydroxypalmitoleic acid, hydroxylinoleic acid, hydroxyarachidonic acid, hydroxyoleic acid, or hydroxyerucic acid; α４１ is a hydroxy-functional C-C 30 linear or branched alkyl), and mercaptoalkanoic acids such as mercaptopropionic acid (R α４１ is a thiol functional C-C 30 and the like. The alkyl groups include, but are not limited to, straight or branched chain alkyl groups.

[0095] X α４１ may be —SH, and examples of such compounds (α41) include alkyl thiols (R α４１ is a C-C group optionally containing at least one unsaturated group 30 and the like. The alkyl groups include, but are not limited to, straight or branched chain alkyl groups.

[0096] X α４１ may be —NH(R′), and examples of such compounds (α41) include alkylamines (R α４１ is a C-C group optionally containing at least one unsaturated group 30 an alkanolamine (R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 2 α４１ is a hydroxy-functional C-C 30 linear or branched alkyl), silicone prepolymer polyamine (R α４１ is an amine-functional linear or branched organosiloxane), alkyldiamine (R α４１ is an amine functional C-C 30 straight-chain or branched-chain alkyl), and aminoalkanesulfonic acids such as 2-aminoethanesulfonic acid (R α４１is HO-S(O)2R α４１４ -), but are not limited to.

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

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

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

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

[0101] [Raw Material Isocyanate] The isocyanate derivative (B) has a moiety derived from the raw material isocyanate.

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

[0103] The aromatic polyisocyanate is a compound having an aromatic ring and an isocyanate group. The aromatic polyisocyanate may have one or more, two or more, or three or more aromatic rings, and may have five or fewer, four or fewer, or three or fewer aromatic rings.

[0104] The acyclic aliphatic polyisocyanate is an aliphatic polyisocyanate that does not have a ring structure. The acyclic aliphatic polyisocyanate may have an aliphatic hydrocarbon group having from 2 to 20 carbon atoms. The aliphatic hydrocarbon group having from 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 aspect, the acyclic aliphatic polyisocyanate may be a polyisocyanate compound having an isocyanate group at the terminal of an alkylene group.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0121] [Amount of Isocyanate Derivative (B)] The amount of the isocyanate derivative (B) may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, per 100 parts by weight of the non-fluorinated copolymer (A). The amount of the isocyanate derivative (B) may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, per 100 parts by weight of the non-fluorinated copolymer (A).

[0122] [Silicone] The water repellent composition of the present disclosure preferably contains silicone in addition to the hydrophobic monomer (a1). By including silicone, the water repellent composition can have both good water repellency and good slip resistance.

[0123] Silicones have the formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 ) ２ -O-] ｂ -Si(R 53 )3 (S1) [wherein, R ５１ each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or an alkoxy group having 1 to 40 carbon atoms; ５３ each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a saturated hydrocarbon group having 1 to 40 carbon atoms, a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 5 to 200.

[0124] R ５１ and R ５３ In the formula (R), the alkyl group having 1 to 40 carbon atoms and the aryl group having 6 to 40 carbon atoms may be unsubstituted or substituted. ５１ and R ５３Specific examples of R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group; a cyclopentyl group, a cyclohexyl group, a cycloheptyl group; a phenyl group, a tolyl group, a naphthyl group, or a group in which some or all of the hydrogen atoms bonded to these groups have been substituted with a halogen atom, an amino group, a cyano group, or the like. ５１ and R ５３ is preferably a methyl group or an ethyl group. ５１ and R ５３ In the formula (I), the alkoxy group having 1 to 40 carbon atoms may be linear or branched. Examples of the alkoxy group having 1 to 40 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

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

[0126] The long-chain hydrocarbon group R is preferred because it is easy to produce industrially and is readily available. ５１ and R ５３ Other than R５１ and R ５３ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0127] a is an integer of 0 or more. In terms of ease of industrial production and availability, a may be 40 or less, 30 or less, or 20 or less, and is preferably 30 or less.

[0128] The sum of a and b is 5 to 200. From the viewpoints of ease of industrial production, availability, and handling, the sum of a and b is preferably 10 to 100, and more preferably 40 to 60. a may be 0 to 150, for example, 1 to 100. The lower limit of b may be 1, 2, or 3, and the upper limit of b may be 150, 10, or 5.

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

[0130] R ５１ and R ５３ group (for example, when represented by the following formula (S2), R ５１ and R ５２ Group and R ５３ It is preferred that 50 mol % or more of the total of the alkyl groups) be methyl groups.

[0131] The order of the repeating units bound by a or b is not limited to the order shown in the chemical formula, and can be any order. That is, the silicone may be a random polymer or a block polymer.

[0132] For example, silicones may be of the formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )(R 52 )-O-] ｂ -Si(R 53 )3 (S2) [wherein, R ５１each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a long-chain hydrocarbon group; ５２ each independently represents a long chain hydrocarbon group; ５３ each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a long-chain hydrocarbon group, a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 5 to 200. In formula (S2), R ５１ and R ５３ may have an alkyl group having 3 to 40 carbon atoms or an unsaturated hydrocarbon group having 6 to 40 carbon atoms (for example, a hydrocarbon group having an aromatic ring), but it is preferable that it does not have these groups.

[0133] Examples of silicones are: [In the formula, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a+b) is an integer of 5 to 200, and n is an integer of 1 to 36 (preferably n is a long-chain hydrocarbon group).]

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

[0135] Examples of silicones containing SiH groups include methylhydrogensilicones with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methylhydrogensiloxane. Among these, methylhydrogensilicones are preferred due to their ease of industrial production and availability. Hydrogensilicones (e.g., methylhydrogensilicones) are polydiorganosiloxanes in which a portion of the side chain is substituted with hydrogen, with the hydrogen atoms directly bonded to silicon atoms. When using hydrogensilicones, a catalyst may be used to improve reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine-based catalysts can be used. Metal salts of organic acids are preferred as catalysts, and fatty acids are preferred as organic acids. From the perspective of easy handling, zinc stearate or the like can be used. The catalyst is preferably used in an amount of 10 to 40% relative to the methylhydrogensilicone, as this facilitates its effectiveness. Two or more of amino-modified, epoxy-modified, carboxy-modified, and methylhydrogensilicones may be mixed. All of these silicones have reactive groups, and it is preferable that they have film-forming properties. The film-forming ability means that after the silicone is attached to the fiber surface in an emulsion state, it forms a solid film, rather than an oily or gel-like film.

[0136] α-olefins are compounds from which long-chain hydrocarbon groups in silicones are derived. Specific examples of α-olefins are 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triacontene, and 1-dotriacontene. The hydrosilylation reaction may be carried out by reacting the α-olefin with the above-mentioned silicone having SiH groups in the presence of a catalyst, either stepwise or all at once.

[0137] The amounts of the SiH group-containing silicone and α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent weight or number average molecular weight of the SiH group-containing silicone.

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

[0139] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted appropriately. The reaction temperature is, for example, 10 to 200°C, preferably 50 to 150°C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150°C. The hydrosilylation reaction is preferably carried out in an inert gas atmosphere. Examples of the inert gas include nitrogen and argon. The reaction proceeds even in the absence of a solvent, but a solvent may also be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0140] (Reactive Silicone) The silicone may contain a reactive silicone. Examples of reactive silicones include polysiloxanes having reactive groups on the side chain, one end, both ends, or the side chain and both ends. From the viewpoint of achieving excellent slip resistance and excellent water repellency at the same time, polysiloxanes having reactive groups on the side chain and / or both ends may also be used. The reactive silicone is not particularly limited as long as it has a reactive group in the molecule, and examples include amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, and hydrogen-modified silicone. The reactive silicone may be one in which one or more substituents in the above formula (S1) or formula (S2) have been replaced with a reactive group.

[0141] Examples of amino-modified silicones include those having a structure in which an amino group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. The alkylene group preferably has 2 or more carbon atoms. The divalent aromatic group preferably has 6 or more carbon atoms. The amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group. Examples of organic groups bonded to an amino group include the following: 2-aminoethyl group, N-methyl-2-aminoethyl group, N,N-dimethyl-2-aminoethyl group, N-ethyl-2-aminoethyl group, N,N-diethyl-2-aminoethyl group, N,N-methylethyl-2-aminoethyl group, 3-aminopropyl group, N-methyl-3-aminopropyl group, N,N-dimethyl-3-aminopropyl group, N-ethyl-3-anopropyl group, N,N-diethyl-3-aminopropyl group, and N,N-methylethyl-3-aminopropyl group. These functional groups may be located on the side chains of the polysiloxane or at the terminals.

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

[0143] Examples of carboxy-modified silicones include those having a structure in which a carboxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. The alkylene group preferably has two or more carbon atoms. The divalent aromatic group preferably has six or more carbon atoms. Examples of such functional groups include a 3-carboxypropyl group and a 2-carboxyethyl group. These functional groups may be present on the side chain of the polysiloxane or at the terminal.

[0144] (Silicone Resin) The silicone may include a silicone resin.３ SiO １／２ Units (M units), RSiO ３／２ Units (T units) and SiO ４／２ The silicone resin (B) is a silicone resin consisting of at least one selected from the group consisting of M units and Q units, where R is a linear or branched monovalent alkyl group having 1 to 18 carbon atoms, and silicone resins consisting of only M units and only Q units are excluded. ２ SiO ２／２ It is preferable that the unit (D unit) is not contained from the viewpoint of exerting the effects of the present invention.

[0145] The silicone resin is preferably in a sol state. Examples of R include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, decyl, cetyl, and stearyl groups, but from the standpoint of stability when the silicone resin (B) is in a sol state, ease of raw material availability, and cost, R is preferably a methyl group, and it is particularly preferred that 90% or more of all R are methyl groups. Note that different types of groups may be used in combination as R.

[0146] Silicone resin with R ２ SiO ２／２ If the silicone resin contains D units, the low slip properties of the water repellent composition may be impaired. Also, if the silicone resin contains only Q units, the water repellent properties of the water repellent composition may be impaired.

[0147] Examples of the silicone resin structure include (i) silicone resins consisting of M units and Q units, (ii) M units, T units and Q units, (iii) M units and T units, (iv) T units and Q units, and (v) silicone resins consisting only of T units. (i) A silicone resin consisting of M units and Q units and (v) a silicone resin consisting only of T units are preferred. (i) The molar ratio of M units to Q units (M / Q) in a silicone resin consisting of M units and Q units is preferably M / Q = 0.6 to 1.3, more preferably M / Q = 0.8 to 1.1. Two or more of these silicone resins may be used in combination.

[0148] The silicone resin (B) may also contain a structural unit containing a hydroxyl group bonded to a silicon atom. Specifically, the structural unit may be (HO)RSiO ２／２ Units and (HO) ２ RSiO １／２ Units: (HO)SiO ３／２ Units, (HO) ２ SiO ２／２ Units, (HO) ３ SiO １／２ A part of the hydroxyl groups may be an alkoxy group represented by an RO group.

[0149] As described in Japanese Patent No. 3,852,921, a sol containing a silicone resin can be obtained by a production method in which an organodisiloxane, a tetraalkoxysilane, and their partial hydrolysis condensates are uniformly dispersed and polymerized in water containing a surfactant, or by a production method in which the following silane compound is hydrolyzed in water.

[0150] The production method of hydrolyzing a silane compound in water will now be described in detail. Any silane compound can be used as a raw material for the production, as long as the hydrolyzable group is chloro or alkoxy, the compound contains one, three, or four hydrolyzable groups, and the compound has an alkyl group that satisfies the above conditions.Specifically, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrichlorosilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrichlorosilane, Trichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrichlorosilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, 2-ethylhexyltrichlorosilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, decyltriethoxysilane, cetyltrichlorosilane, cetyltrimethoxysilane, cetyltriethoxy Silane, stearyl trichlorosilane, stearyl trimethoxysilane, stearyl triethoxysilane, trimethyl chlorosilane, trimethyl methoxysilane, trimethyl ethoxysilane, trimethyl isopropoxysilane, dimethyl ethyl chlorosilane, dimethyl ethyl methoxysilane, dimethyl ethyl ethoxysilane, dimethyl propyl chlorosilane, dimethyl propyl methoxysilane, dimethyl propyl ethoxysilane, dimethyl isopropyl chlorosilane, dimethyl isopropyl methoxysilane, dimethyl isopropyl ethoxysilane, di Usable silane compounds include, but are not limited to, methylhexyl chlorosilane, dimethylhexyl methoxysilane, dimethylhexyl ethoxysilane, dimethyldecyl chlorosilane, dimethyldecyl methoxysilane, dimethyldecyl ethoxysilane, dimethyl cetyl chlorosilane, dimethyl cetyl methoxysilane, dimethyl cetyl ethoxysilane, dimethylstearyl chlorosilane, dimethylstearyl methoxysilane, dimethylstearyl ethoxysilane, and partial hydrolysates thereof.From the viewpoints of operability, ease of distilling off by-products, and ease of obtaining raw materials, it is more preferable to use methoxysilane or ethoxysilane. One or a mixture of two or more of these silane compounds may be used.

[0151] Conventional methods can be used to hydrolyze silane compounds in water. These methods include dripping the silane compound into water and then carrying out the hydrolysis reaction, or mixing water and the silane compound together and then carrying out the hydrolysis reaction. A hydrolysis catalyst may be used in carrying out the hydrolysis reaction. Conventional catalysts can be used as the hydrolysis catalyst, preferably acidic or alkaline. Acidic catalysts include hydrogen halides, carboxylic acids, sulfonic acids, acidic or weakly acidic inorganic salts, and solid acids such as ion exchange resins. Alkaline catalysts include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate; alkali metal silanolates such as sodium silanolate and potassium silanolate; amines such as triethylamine, diethylamine, and aniline; and aqueous ammonia. The amount of catalyst added is preferably adjusted so that the pH of the aqueous solution is between 2 and 7 or between 7 and 12. After the reaction is complete, a neutralizing agent may be added to neutralize the acidic or alkaline catalyst, if necessary.

[0152] A surfactant may be added to the aqueous solution to disperse the silane compound and the hydrolysis reaction product in water. The surfactant is not particularly limited, but examples include anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, and alkyl phosphates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene oxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and polyoxyethylene fatty acid esters; cationic surfactants such as quaternary ammonium salts and alkylamine acetates; and amphoteric surfactants such as alkyl betaines and alkyl imidazolines. These surfactants can be used alone or in combination of two or more. Surfactants that exhibit acidic or alkaline properties can also be used as hydrolysis catalysts. The amount of surfactant added is not particularly limited, but preferably 1 to 50 parts by weight per 100 parts by weight of the silane compound. Adding less than 1 part by weight of the surfactant will not fully achieve its intended effect, while adding more than 50 parts by weight may impair the water repellency of the water repellent agent.

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

[0154] (Amount of Silicone) The amount of silicone may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the non-fluorine-containing copolymer (A). The amount of silicone may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the non-fluorine-containing copolymer (A).

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

[0156] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, animal and vegetable wax, and mineral wax. Paraffin wax is preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane), and normal alkenes (e.g., 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane). The number of carbon atoms in the compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500, or 300 to 1000. These may be used alone or in combination of two or more.

[0157] The melting point of the wax may be 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher, preferably 55° C. or higher, more preferably 60° C. or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0158] (Amount of Wax) The amount of wax may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the non-fluorinated copolymer (A). The amount of wax may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the non-fluorinated copolymer (A).

[0159] [Inorganic Particles] The water repellent composition of the present disclosure may contain inorganic particles. By including inorganic particles, water repellency and slip resistance can be better imparted. The inorganic particles may be aluminum compounds (e.g., alumina), silicon compounds (e.g., silica), titanium compounds, etc. These may be used alone or in combination of two or more. The inorganic particles may be subjected to a hydrophilic surface treatment or a hydrophobic surface treatment.

[0160] The average primary particle diameter of the inorganic particles may be 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, or 30 nm or more. The average primary particle diameter of the inorganic particles may be 600 nm or less, 400 nm or less, 200 nm or less, 100 nm or less, 40 nm or less, 37.5 nm or less, 35 nm or less, 32.5 nm or less, 30 nm or less, 27.5 nm or less, 25 nm or less, or 22.5 nm or less, preferably 40 nm or less. Being within the above range can achieve good water repellency and slip resistance. The average primary particle diameter can be measured using a microscope (scanning electron microscope or transmission electron microscope). Specifically, an arbitrary position on the fabric is observed from above using a microscope at an arbitrary magnification. Next, if the particle shape is spherical, the diameter is considered to be the particle diameter (particle size), and if the particle shape is non-spherical, the average of the longest and shortest diameters is considered to be the particle size (particle size). The particle diameters of all particles present within the field of view are measured, and then the field of view is moved and the particle diameters are measured again. This process is repeated to measure particle diameters at 10 or more points, and the average value is taken as the average primary particle diameter.

[0161] (Amount of inorganic particles) The amount of inorganic particles may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the non-fluorine copolymer (A). The amount of inorganic particles may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the non-fluorine copolymer (A).

[0162] [Liquid Medium] The water repellent composition may contain a liquid medium. The liquid medium is water, an organic solvent, or a mixture of water and an organic solvent. A mixture of water and an organic solvent is preferred. By including an organic solvent, the water repellent composition can have both good water repellency and slip resistance.

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

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

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

[0166] The amount of organic solvent may be 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 40% by weight or more, based on the liquid medium. The amount of organic solvent may be 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, 12.5% ​​by weight or less, 7.5% by weight or less, or 5.0% by weight or less, based on the liquid medium.

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

[0168] The amount of the organic solvent may be 0.5 parts by weight or more, 1 part by weight or more, 1.5 parts by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, or 40 parts by weight or more, relative to 100 parts by weight of water. The amount of the organic solvent may be 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 25 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of water.

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

[0170] (Amount of Dispersant) The amount of the dispersant may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the non-fluorinated copolymer (A). The amount of the dispersant may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the non-fluorinated copolymer (A).

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

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

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

[0174] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to hexa-hydric (particularly di- to penta-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0175] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to hexa-hydric (particularly di- to penta-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0176] Examples of alkanolamides are those formed from fatty acids and alkanolamines. The alkanolamides may be monoalkanolamides or dialkanolamines. Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

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

[0178] The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably 2 to 100. The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.

[0179] The nonionic surfactant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide adduct moiety and the polyalkylene glycol moiety is polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, due to environmental concerns (biodegradability, endocrine disrupters, etc.), it is preferable that the nonionic surfactant have a structure that does not contain an aromatic group.

[0180] The nonionic surfactant has the formula: 1 O-(CH ２ CH ２ O) p -(R 2 O) q -R 3 [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms, 2 are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more.

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

[0182] Specific examples of nonionic surfactants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C １２ -C １６ ) thiol, sorbitan mono fatty acid (C ７ -C １９ ) or alkyl (C １２ -C １８ ) condensation products with amines, etc.

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

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

[0185] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene adduct ammonium salt. Specific examples of the cationic surfactant include, but are not limited to, amine salt surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, and quaternary ammonium salt surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride.

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

[0187] The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula: 1 p - N + R 2 q X － [In the formula, R 1 is C12 or higher (e.g., C １２ ~C ５０ ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, especially 3) to 50) (CH3 and C2H5 are particularly preferred), X is a halogen atom (for example), a C1-C4 fatty acid base, p is 1 or 2, q is 2 or 3, and p+q=4.] R １ may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0188] Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0189] Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid type surfactants, phosphoric acid mono- or diester type surfactants, and sulfosuccinate esters.

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

[0191] The surfactant may be a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant, each of which may be one type or a combination of two or more types.

[0192] (Amount of Surfactant) The amount of surfactant may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, per 100 parts by weight of the non-fluorinated copolymer (A). The amount of surfactant may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, per 100 parts by weight of the non-fluorinated copolymer (A). The amount of cationic surfactant may be 5% by weight or more, preferably 10% by weight or more, and more preferably 20% by weight or more, per the total amount of surfactants. The weight ratio of the nonionic surfactant to the cationic surfactant is preferably 95:5 to 20:80, more preferably 85:15 to 40:60. The amount of cationic surfactant may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight, per 100 parts by weight of the water-repellent resin. The total amount of the surfactant may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight, relative to 100 parts by weight of the water-repellent resin.

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

[0194] The curing agent (crosslinking agent) in the water repellent composition can satisfactorily cure the fluorine-free copolymer (A). The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive group of the fluorine-free copolymer (A). Examples of the active hydrogen-reactive compound include polyisocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound include hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

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

[0196] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate, Aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0197] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

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

[0199] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

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

[0201] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable in aqueous solution and can be used in the same aqueous solution as the water repellent composition.

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

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

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

[0205] (Amount of Curing Agent) The amount of curing agent may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the non-fluorinated copolymer (A). The amount of curing agent may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the non-fluorinated copolymer (A).

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

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

[0208] (Antistatic Agent) Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate ester salts, phosphonates, and phosphate ester salts; amphoteric antistatic agents such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, and nonionic antistatic agents such as aminoalcohols and its derivatives, glycerin and its derivatives, and polyethylene glycol and its derivatives. Ionic conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ionic conductive groups may also be used. These may be used alone or in combination of two or more.

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

[0210] Amine-based solvents such as Bis (3-aminopropyl) dodecylamine (trialkyltriamine), Alcohol-based solvents such as Ethyl alcohol (ethyl alcohol, ethanol), Iso-propyl alcohol (isopropanol), Propyl alcohol (propyl alcohol, propanol), Tris (hydroxymethyl) nitromethane (trisnitro), 1,1,1-Trichloro-2-methyl-2-propanol (chlorobutanol), 2-Bromo-2-nitropropane-1,3-diol (Pronobol, Pronozole, Pronocot), Aldehyde-based solvents such as 1,5-Pentanediol (glutaraldehyde), Formaldehyde, α-Bromocinnamic aldehyde, Isothiazolin-based compounds such as 2-n-Octyl-4-isothiazolin-3-one (Skein M-8), 5-Chloro-2-methyl-4-isothiazolin-3-one / 2-Methyl-4-isothiazolin-3-one (Caisson CG, NS-500W), 1,2-Benzisothiazolone-3 (BIT), and N-n-Butyl-1,2-benzisothiazolone-3 (n-butyl BIT); isothiocyanate-based compounds such as allyl isothiocyanate (aryl isothiocyanate, allyl isothiocyanate); imidazole-based compounds such as 2-(4-Thiazolyl)-benzimidazol (thiabendazole, TBZ) and methyl-2-benzimidazole carbamate (2-benzimidazolyl methyl carbamate, Preventol BCM); Glycerol laurate (lauricidin, glyceryl monolaurate, monoglyceride), oxazolidines such as 4,4-Dimethyl-1,3-oxazolidine (Biopan CS-1135, Oxazine A), 3,4,4'-Trichlorocarbanilide (triclocarban, trichlorocarbanilide), 4,Carbanilides such as 4'-Dichloro-3-(3-Fluoromethyl)-carbanilide (halocarban, cloflucarban), carbamates such as 3-Iodo-2-propynylbutyl carbamate (Glycical), Benzoic acid (benzoic acid, benzenecarboxylic acid), Flexa-2,4-dienoic acid (sorbic acid, 2-propanylacrylic acid), Octanoic acid (caprylic acid), Propionic acid, Undecylenic acid (10-undecylenic acid, 10-undecenoic acid), Potassium hexa-2,4-dienoic acid (potassium sorbate, potassium 2-propenylacrylic acid), Potassium propionate (potassium propionate), Calcium propionate (calcium propionate), Sodium benzoate (sodium benzoate), Sodium propionate (sodium propionate), Magnesate(2-),bis(2-carboxybenzene Carboxylic acid-based compounds such as 8-Hydroxyquinoline and Bis(quinolin-8-olate) copper (quinoline copper, oxine copper, 8-quinolinol copper); Sulfide-based compounds such as Bis(dimethylthiocarbamoyl)disulfide (TMTD, thiuram); Diphenyl ether-based compounds such as 2,4,4'-Trichloro-2'-hydroxydiphenyl (triclosan, Irgasan DP300); N,N-Dimethyl-N'-(fluorodichloromethylthio)-N"-phenylsulfamide (cyclofluanid, Preventol A4-S), N-Dichlorofluoromethylthio-N',Sulfamides such as N'-dimethyl-N-p-torylsulfamide (triflamide, Preventol A5), protein-based compounds such as Protamine (milt protein, milt hydrolysate, nuclear protein) and Hen egg lysozyme, thiazole-based compounds such as 2-(4-Thiocyanomethylthio)benzothiazol, thiocarbamate-based compounds such as Sodium N-methyldithiocarbamate (N-methyldithiocarbamate sodium, carbam sodium), Hexahydro-1,3,5-tris(hydroxyethyl)-S-triadine (Biopan GK, triazine), Triazines such as CAVINON (100,200) and α-[2-(4-Chlorophenyl)ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol (devconazole), tropolones such as 4-Isopropyl-2-hydroxy-cyclohepta-2,4,6-triene-1-one (hinokitiol, β-thujaplicin), nitriles such as 2,4,5,6-Tetrachloroisophthalonitrile and 1,2-Dibromo-2,4-dicyanobutane (Tectoramal 38), 1,1'-(Hexamethylene bis[5-(4-chlorophenyl)biguanide]digluconate (chlorhexidine glucuronate), Bis(p-chlorophenyldiguanide)hexane biguanides such as chlorhexidine hydrochloride, 1-Bromo-3-chloro-5,5'-dimethyl hydantoin, 1,3-Bis-(hydroxymethyl)-5,Hydantoin-based compounds such as 5'-dimethyl hydantoin (Glidant, Dantoguard), pyridine-based compounds such as Sodium pyridine thiol-1-oxide (pyrithione sodium), Zinc bis(2-pyridylthio-1-oxide) (zinc pyrithione, zincomadine, ZPT), 2,3,5,6-Tetrachloro-4-(methylsulphonyl)pyridine (densil), and Copper bis(2-pyridylthio-1-oxide) (copper pyrithione, copperomadine, CuPT), Phenols such as 2-Isopropyl-5-methylphenol (thymol, 2-isopropyl-5-methylphenol), 3-Methyl-4-isopropylphenol (isopropylmethylphenol, piosol), o-Phenylphenol (OPP, orthophenylphenol), Phenol (phenol, carbolic acid), Butyl-p-hydroxybenzoate (butylparaben), Ethyl-p-hydroxybenzoate (ethylparaben), Methyl-p-hydroxybenzoate (methylparaben), Propyl-p-hydroxybenzoate (propylparaben), m-Methylphenol (metacresol), o-Methylphenol (orthocresol), p-Methylphenol (paracresol), o-Phenylsodiumphenoxide (sodium orthophenylphenol), 2-Benzyl-4-chlorophenol (chlorophene), p-Chlorophenol (parachlorophenol), 4-Chloro-3,5-dimethylphenol (parachlorometaxylenol), and 2-Methyl-3-chlorophenol (parachlorometacresol), Phthalimide-based compounds such as N-(Fluorodichloromethylthio)-phthalimide (Fluorofolpet, Briventol A3), peptide-based compounds such as ε-Poly-L-lysine (Polylysine, ε-Polylysine), 4-(2-Nitrobutyl)morpholine / 4,Morpholine-based agents such as 4'-(2-nitrotrimethylene)dimorpholine (Biopan P-1487); iodine-based agents such as Diiodomethyl-p-trylsulfone (diiodidemethyl-p-trylsulfone), Polyvinylpyrolidone iodide (Povidone iodine, Isodine), p-Chlorophenyl-3-iodopropagyl formal (parachlorophenyl-3-iodide propagyl formal), and 3-Bromo-2,3-diiodo-2-propenylethylcarbonate (Sunplus); chlorine-based agents such as Sodium hypochlorite (sodium hypochlorite), Sodium dichlorinated isocyanurate (sodium dichloroisocyanurate), and Trichlorinated isocyanuric acid; peroxide-based agents such as Hydrogen peroxide, Chlorine dioxide (stabilized chlorine dioxide, Biotoke), and Peracetic acid; Metal salts such as copper naphthenate, silver / zirconium phosphate (Novalon AG300), silver chloride / titanium oxide, silver-zinc / calcium phosphate (silver Ace), silver-zinc / zeolite (silver zinc aluminosilicate, silver zinc zeolite), zinc oxide, silver / zirconium phosphate (Novalon AGZ330), and N-Stearoyl-L-glutamic acid AgCu salt (Pholon Killer); antibiotics such as 1-L-(1,3,5 / 2,4)-1,5-Diamino-4-O-(2,5-dideoxy-α-D-glucopyranosyl)-2,3-cyclohexandiol (ST-7); oxides such as ethylene oxide (EO) and propylene oxide (PO);4'-(Tetramethylenedicarbonyldiamino)bis(1-decylpyridinium bromide) (dimer 135), Decyldimethylbenzylammonium chloride (benzalkonium chloride), Didecyldimethylammonium chloride (didecyldimethylammonium chloride, Bardac 2250 / 80), Diisobutylphenoxyethoxydimethylbenzylammonium chloride (benzothonium chloride, Hyamine 1622), Hexadecyl trimethyl ammonium bromide (cetylammonium bromide, cetrimide, CTAB, Secbron), N,N'-Hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide) (dimer 38), N-Alkyl-N,N-dimethyl-N-benzylammonium chloride (benzalkonium chloride, Hyamine 3500J), N-Decyl-N-isononyl-N,N'-dimethylammonium Examples of suitable antibacterial and antifungal agents include quaternary ammonium salts such as hexadecyl pyridinium chloride (Bardac 170P), 5-(trimethoxysilyl)propyldimethyloctadecylammonium (DC-5700), and hexadecyl pyridinium chloride (cetylpyridinium chloride), carbohydrates such as β-1,4-poly-D-glucosamine (chitosan), and ureas such as N'-(3,4-dichlorophenyl)-N,N-dimethylurea (Duuron, DCMU, Briventol A6). Particularly preferred are isothiazolin-based antibacterial and antifungal agents such as 2-n-octyl-4-isothiazolin-3-one (Skein M6), a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one (BIT), and N-n-butyl-1,2-benzisothiazolin-3-one (BBIT). ,

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

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

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

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

[0215] (Preservatives) Preservatives that can be used mainly to enhance antiseptic and bactericidal properties and maintain antiseptic properties during long-term storage include, for example, isothiazolinone-based organic sulfur compounds, benzisothiazoline-based organic sulfur compounds, benzoic acids, 2-bromo-2-nitropropane-1,3-diol, etc. The amount of preservative is preferably 0.0001 to 1 wt % relative to the total weight of the water repellent composition. When the amount of preservative is equal to or greater than the lower limit of the above range, the effect of adding the preservative is sufficient, and when the amount is equal to or less than the upper limit, the storage stability of the water repellent composition is good.

[0216] (Antibacterial Agent) An antibacterial agent is a component that has the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors resulting from microbial decomposition products. Examples of the antibacterial agent include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylenebiguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0217] (Ultraviolet Absorber) An ultraviolet absorber is a chemical agent that has the effect of protecting against ultraviolet rays, and is a component that absorbs ultraviolet rays and converts them into infrared rays, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

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

[0219] (Fragrance) The fragrance is not particularly limited, and a list of usable fragrance raw materials can be found in various documents, for example, "Perfume and Flavor Chemicals", Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994), "Synthetic Fragrances: Chemistry and Product Knowledge", Indo Genichi, The Chemical Daily Co. (1996), and "Perfume and Flavor Materials of Natural Origin", Steffen Arctander, Allured Pub. Co. (1994), "Encyclopedia of Fragrance," edited by the Japan Fragrance Association, Asakura Shoten (1989), "Perfume 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., each of which is incorporated herein by reference.

[0220] (Amount of Other Components) The amount of the other components may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the non-fluorinated copolymer (A). The amount of the other components may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the non-fluorinated copolymer (A).

[0221] <Method for producing water repellent composition> The method for producing a water repellent composition includes copolymerizing a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms with at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride in the presence of an isocyanate derivative (B) to obtain a fluorine-free copolymer (A). The water repellent composition of the present disclosure can be obtained by this method (hereinafter referred to as Method 1).

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

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

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

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

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

[0227] In emulsion polymerization, the organic acid listed above may be added. For example, the organic acid may be a carboxylic acid such as acetic acid. The organic acid may be, for example, 0.01 parts by weight or more, 0.1 parts by weight or more, or 1 part by weight or less, 0.5 parts by weight or less, relative to 100 parts by weight of the total amount of the monomers.

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

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

[0230] The above-mentioned surfactants can also be used as the emulsifier.

[0231] The emulsifier may also contain a reactive emulsifier. In the case where the emulsifier contains a reactive emulsifier, the fluorine-free copolymer (A) (polymer of the above-mentioned monomers) becomes a polymer containing structural units derived from the reactive emulsifier.

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

[0233] The reactive emulsifier is a radically reactive emulsifying dispersant, i.e., an emulsifier having one or more polymerizable unsaturated groups in the molecule, and is copolymerizable with the above-mentioned monomer. Examples of the reactive emulsifier include the reactive emulsifiers described in JP 2017-25440 A, and preferably the reactive emulsifier represented by the following formula:

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

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

[0236] If the reactive emulsifier is a reactive emulsifier represented by the above formula, the product stability of the aqueous dispersion (repellent composition) is improved without reducing the water repellency.Preferably, the reactive emulsifier represented by the above formula is polyoxyethylene alkylphenol or the like.

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

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

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

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

[0241] After mixing the above-mentioned components, the mixture is stirred and subjected to ultrasonic waves to emulsify the mixture.

[0242] As a method for stirring, for example, a dispersing machine such as a homomixer, an ultrasonic homogenizer, a pressure homogenizer, a milder, or a porous membrane press-in dispersing machine is used, and preferably a homomixer is used.

[0243] Stirring conditions are appropriately set. When a homomixer is used, the rotation speed is set to, for example, 500 rpm or more and, for example, 10,000 rpm or less. The stirring time is, for example, 0.5 minutes or more and, for example, 10 minutes or less, preferably 5 minutes or less. The stirring temperature is, for example, 50°C or more and, for example, 90°C or less.

[0244] Next, if a portion of the monomers was blended when preparing the above-mentioned mixed solution, the remaining portion of the above-mentioned monomers is blended into this mixed solution.

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

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

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

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

[0249] Examples of the chain transfer agent include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite, and preferably lauryl mercaptan.

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

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

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

[0253] In the first method, the monomers constituting the above-mentioned non-fluorinated copolymer (A) are polymerized in the presence of the isocyanate derivative (B), but it is also possible to polymerize the monomers and then blend the isocyanate derivative (B) (second method).Alternatively, it is also possible to polymerize the monomers in the presence of a surfactant and a liquid medium and then blend the isocyanate derivative (B) (third method).

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

[0255] Alternatively, a method may be adopted in which a non-fluorinated copolymer (A) is prepared by polymerizing a monomer, and then the obtained non-fluorinated copolymer (A) is blended with an isocyanate derivative (B) (fourth method). Alternatively, a method may be adopted in which a non-fluorinated copolymer (A) is prepared by polymerizing a monomer, and then the obtained non-fluorinated copolymer (A) is blended with an isocyanate derivative (B), a surfactant, and a liquid medium (fifth method).

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

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

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

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

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

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

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

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

[0264] <Applications of Water Repellent Composition> Examples of applications of the water repellent composition according to the present disclosure include an external treatment agent (surface treatment agent) or an internal treatment agent, a repellent (a water repellent, an oil repellent, or a water and oil repellent, etc., particularly a water repellent), an antifouling agent, a soil release agent, a stripping agent, a release agent (an external release agent or an internal release agent), and the like.

[0265] <Method for Producing Treated Product> The method for producing a treated product in the present disclosure includes a step of applying the water repellent composition of the present disclosure to a substrate (particularly a fibrous substrate).

[0266] [Treated Products] Substrates that can be treated with the water repellent composition of the present disclosure include textiles, stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Various examples of textile products can be mentioned. Examples include natural fibers of animal and plant origin such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber; and mixtures thereof. Woven and knitted fabrics are described in detail below as an example of a substrate that can be treated with the water repellent composition.

[0267] (Woven / knitted fabric) - Manufacturing method of knitted / knitted fabric Woven / knitted fabrics can be obtained by weaving and knitting the mixed / entangled yarn to obtain a gray fabric, and then post-processing and water-repellent processing the same. The weaving and knitting can be performed using a known loom and knitting machine, and the preparation process prior to the weaving and knitting can also be performed using known equipment.

[0268] In the post-processing, the grey fabric is first scoured and relaxed. The scouring and relaxation may be carried out by a continuous or batch method at a temperature of 80 to 130°C. Usually, it is preferable to carry out the scouring and relaxation by a batch method at 100°C or less, and it is particularly preferable to carry out the scouring and relaxation using a high-pressure jet dyeing machine equipped with a jet nozzle.

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

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

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

[0272] The woven / knitted fabric of the present disclosure may be provided as a laminated fabric having a moisture-permeable waterproof layer on one side thereof. The moisture-permeable waterproof layer may be laminated directly onto the woven / knitted fabric, or may be laminated onto the woven / knitted fabric via an adhesive layer. When the laminated fabric of the present disclosure is used for clothing or the like, it is positioned so that the woven / knitted fabric side is exposed to rainwater or the like.

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

[0274] The moisture-permeable waterproof layer may be formed by applying a resin (the resin that constitutes the moisture-permeable waterproof layer) directly to the woven / knitted fabric, or may be laminated on one side of the woven / knitted fabric via an adhesive layer, which will be described later. In the present disclosure, a mixed fiber interlaced yarn having minute protrusions due to loops or slack is used in the woven / knitted fabric. Therefore, the protrusions are firmly entangled with the adhesive layer or the moisture-permeable waterproof layer, thereby creating an anchoring effect, making it even more difficult for the woven / knitted fabric and the moisture-permeable waterproof layer to peel off. If a normal woven / knitted fabric (a woven / knitted fabric in which the above-mentioned protrusions are not sufficiently maintained on the surface) is used, the anchoring effect may not be fully exerted, and in such cases, the woven / knitted fabric and the moisture-permeable waterproof layer tend to peel off easily.

[0275] The resin constituting the moisture-permeable waterproof layer is not particularly limited, but is preferably composed primarily of polyurethane resin, and preferably contains 80% or more by weight of polyurethane resin. Polyurethane resins are generally suitable for forming resin layers that are moisture-permeable and waterproof. In particular, microporous types are preferred in terms of moisture permeability, but if the product is expected to be exposed to rain for long periods of time or to be used repeatedly through washing, etc., non-porous moisture-permeable urethane may be used instead of the microporous type.

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

[0277] The moisture-permeable waterproof layer may have a microporous structure or a non-porous structure. When the moisture-permeable waterproof layer has a microporous structure, the layer may contain an inorganic fine powder to ensure the desired moisture permeability.

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

[0279] The thickness of the moisture-permeable waterproof layer is preferably 5 μm or more, and more preferably 10 to 30 μm. A thickness within this range provides an excellent balance between waterproofness and moisture permeability, and is also advantageous in terms of texture and tear strength.

[0280] Adhesive Layer The laminated fabric preferably includes an adhesive layer. That is, the woven / knitted fabric and the moisture-permeable waterproof layer are preferably laminated via an adhesive layer. The reason for this is described below. In the present disclosure, as described above, the woven / knitted fabric has minute protrusions on its surface due to loops or slack. Therefore, the protrusions are firmly entangled with the adhesive layer, which creates an anchor effect, making it even more difficult for the woven / knitted fabric and the moisture-permeable waterproof layer to peel off.

[0281] Furthermore, when a moisture-permeable waterproof layer is directly laminated to the above-mentioned woven or knitted fabric, for example, by a coating method, the protrusions on the surface of the woven or knitted fabric may penetrate the moisture-permeable waterproof layer, resulting in the formation of pinholes and reduced water resistance and strength. There is also a concern that the coating may not be uniform, resulting in uneven thickness of the moisture-permeable waterproof layer. If attempts are made to smooth the surface of the woven or knitted fabric by, for example, calendaring to prevent this, the protrusions or air-retaining layer may be reduced, resulting in reduced water repellency. Therefore, in the present disclosure, it is preferable to laminate the woven or knitted fabric and the moisture-permeable waterproof layer via an adhesive layer.

[0282] The type of adhesive that constitutes the adhesive layer is not particularly limited, but it is preferable that it is one that has excellent compatibility with the moisture-permeable waterproof layer. For example, if a resin containing polyurethane resin as the main component is selected as the resin that constitutes the moisture-permeable waterproof layer, it is preferable to use an adhesive layer made of a polyurethane-based adhesive. The polyurethane-based adhesive may be any of ether-based, ester-based, polycarbonate-based, etc., but from the viewpoint of imparting excellent moisture permeability, an ether-based adhesive is preferable.

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

[0284] The thickness of the adhesive layer is preferably about 10 to 100 μm, more preferably 20 to 80 μm. If the thickness is less than 10 μm, it is difficult to obtain a durable laminated fabric even if the adhesive occupies a large area, and if it exceeds 100 μm, not only will the manufacturing cost increase but further adhesiveness will also tend to be difficult to expect, so neither is preferable.

[0285] - Lining fiber fabric In the laminated fabric of the present disclosure, a lining fiber fabric may be laminated on the moisture-permeable waterproof layer (on the side of the moisture-permeable waterproof layer opposite to the side on which the woven or knitted fabric of the present disclosure is laminated). The lining fiber fabric can protect the moisture-permeable waterproof layer, thereby achieving even better waterproofness (water pressure resistance) and strength. Furthermore, laminating the lining fiber fabric can suppress elongation of the entire laminated fabric, thereby suppressing reduction of the protruding portions of the mixed fiber composite yarn that would otherwise be pulled by elongation of the woven or knitted fabric due to tension during the finishing process after lamination or when worn, and thereby maintaining the above-mentioned water repellency at a higher level. Furthermore, laminating the lining fiber fabric can further improve water repellency.

[0286] Examples of lining fiber fabrics include various woven and knitted fabrics. Knitted fabrics are particularly suitable because, compared to woven fabrics, the constituent yarns tend to protrude from the surface, resulting in an uneven surface, and the knitted fabric exhibits a stronger anchoring effect, making it less likely to peel from the moisture-permeable waterproof layer. Tricot knitted fabrics are particularly preferred because they have less stretchability than knitted fabrics with other structures, preventing excessively large stitch gaps and enabling more effective water repellency. Tricot knitted fabrics are also preferred because they can be knitted to produce long gray fabrics with fewer seams, allowing them to be evenly layered on the moisture-permeable waterproof layer.

[0287] The material of the fibers constituting the lining fiber fabric is not particularly limited and can be selected as appropriate, but nylon fiber is preferred. This is because acid dyes are generally used in nylon fibers, which makes it less likely for the disperse dye to migrate and sublimate into the moisture-permeable waterproof layer, a problem that occurs with polyester fibers, etc., which use disperse dyes. The form (long fiber, short fiber, or spun yarn) or fineness of the fibers constituting the lining fiber fabric is not particularly limited and can be selected as appropriate as long as the effects of the present disclosure are not impaired.

[0288] Characteristics of the Laminated Fabric The laminated fabric has excellent waterproofness. A suitable example of the waterproofness of the laminated fabric of the present disclosure is a water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method) of, for example, 10,000 mm or more, preferably 15,000 mm or more, more preferably 16,000 mm or more, and particularly preferably 20,000 mm or more. The upper limit of the water level is not particularly limited, but examples thereof include 50,000 mm or 25,000 mm.

[0289] The laminated fabric has excellent moisture permeability. A preferred example of the moisture permeability of the laminated fabric of the present disclosure is a moisture permeability of, for example, 10,000 g / m2, as measured in accordance with JIS L 1099:2012 B-1 method (potassium acetate method). 2 24 hours or more, preferably 15,000 g / m 2 24 hours or more, more preferably 20,000 g / m 2 The upper limit of the moisture permeability is not particularly limited, but is, for example, 40,000 g / m 2 24h or 35,000g / m 2 ・24h・mm is an example.

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

[0291] - Manufacturing method of laminated fabric There are no particular limitations on the manufacturing method of the laminated fabric, and examples include the first manufacturing method and the second manufacturing method shown below. First manufacturing method: Includes a step of forming the moisture-permeable waterproof layer by applying a resin that constitutes the moisture-permeable waterproof layer to the surface of a woven or knitted fabric. Second manufacturing method: Includes a step of forming an adhesive layer on the woven or knitted fabric or the moisture-permeable waterproof layer, and a step of bonding the woven or knitted fabric and the moisture-permeable waterproof layer together via the adhesive layer.

[0292] It is preferable that the woven / knitted fabric used in the laminated fabric (i.e., the woven / knitted fabric of the present disclosure described above) maintain protrusions on the fabric surface as much as possible. For example, if the woven / knitted fabric is subjected to a calendering process to facilitate coating or other processes, the fine protrusions of the mixed / entangled yarns are crushed to form a flat surface, which may prevent a specific water droplet rolling angle from being achieved. Furthermore, if the calendering process is performed, the air retention layer described above may not be sufficiently maintained, and the desired water repellency may not be achieved. Therefore, it is preferable to carefully consider the calendering conditions. For example, when calendering a woven / knitted fabric, normal conditions (e.g., a temperature of 130°C or higher and a linear pressure of 200 to 20,000 N / cm) may be used so as not to excessively reduce the protrusions of the mixed / entangled yarns. Calendering may also be performed without heating.

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

[0294] In the second manufacturing method, examples of the method for forming an adhesive layer on a woven or knitted fabric or a moisture-permeable waterproof layer include a lamination method. In the lamination method, a resin solution or a hot melt method can be used to form the adhesive layer. First, a moisture-permeable waterproof layer-forming resin composition (e.g., a resin composition containing a resin and an organic solvent) is applied to the surface of a release material (such as release paper, release cloth, or release film) with a clearance, and a moisture-permeable waterproof layer is formed while adjusting the thickness, followed by heat treatment to completely react the layer and obtain a film. The release material can be removed as appropriate after lamination or aging.

[0295] An adhesive layer is then formed on the woven or knitted fabric or the moisture-permeable waterproof layer. For example, in the case of a method using a resin solution, a two-component curing polyurethane resin solution adjusted to a viscosity in the range of 500 to 5,000 mPa·s may be applied to the entire surface or in a pattern. The resulting solution is then dried to form an adhesive layer, and the woven or knitted fabric and the moisture-permeable waterproof layer are bonded together via the adhesive layer, and the two are then pressure-bonded or thermocompression-bonded, thereby completing the second manufacturing method.

[0296] On the other hand, in the case of hot melt, it is preferable to use a moisture-curing resin that reacts with moisture in the air, and in practice, it is more preferable to use one that melts in a temperature range of about 80 to 150°C. In this case, the hot melt resin is first melted while taking into consideration the melting point of the resin and its viscosity when melted. The molten resin is then applied to the woven or knitted fabric or the moisture-permeable waterproof layer and allowed to mature while cooling at room temperature to form an adhesive layer. The woven or knitted fabric and the moisture-permeable waterproof layer are then bonded together via the adhesive layer and pressure-bonded, thereby completing the second manufacturing method.

[0297] It is preferable to adopt the second manufacturing method as the manufacturing method. This is because, when a moisture-permeable waterproof layer is laminated using a coating method, there is a concern that pinholes will occur in the moisture-permeable waterproof layer due to fine protrusions on the surface of the woven or knitted fabric, which will tend to reduce water pressure resistance. Furthermore, when a woven or knitted fabric is subjected to a calendering process in an attempt to form a uniform moisture-permeable waterproof layer, there is a concern that the protrusions or air retaining layer will be reduced and the desired water repellency will not be achieved. Furthermore, since careful examination of the calendering conditions is required separately, the process itself may become complicated.

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

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

[0300] [Treatment Method] The water repellent composition of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The water repellent composition of the present disclosure may be dispersed and diluted in an organic solvent or water, if necessary, and applied to the surface of the substrate by a known method such as dip coating, spray coating, foam coating, or the like, followed by drying. After drying, a textile product is obtained to which the solid components of the water repellent composition are attached. If necessary, the composition may be applied together with an appropriate crosslinking agent and cured. Furthermore, the water repellent composition of the present disclosure may be used in combination with various additives such as water and / or oil repellents, antislip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, and antifoaming agents. Examples of the various additives may be the same as those described above under "Other Components" for the water repellent composition. The concentration of the fluorine-free copolymer (A) in the treating agent to be brought into contact with the substrate may be varied depending on the application, but may be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

[0301] [Textile Products] Various examples of textile products serving as substrates include cloth products and paper products. Textile products serving as substrates are also called fiber substrates.

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

[0303] Examples of paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine paper, recycled corrugated cardboard or deinked recycled paper, paper containers, paper molded articles, etc. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating mediums, neutral white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc.

[0304] The water repellent composition can be applied to a textile by any of the known methods for treating textiles (e.g., fabrics) with a liquid. The textile may be immersed in the water repellent composition, or the solution may be applied or sprayed onto the textile. The treated textile is preferably dried and cured by heating to develop water repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

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

[0306] The treated textile may be fabric, including woven fabric, knitted fabric, and nonwoven fabric, clothing fabric, carpet, etc., but may also be fiber or yarn or intermediate textile (e.g., sliver or roving, etc.). The water repellent composition of the present disclosure is particularly effective in making textiles (e.g., synthetic fibers) water repellent.

[0307] The fibers constituting the textile product may be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers or inorganic fibers. The fibers may be used alone or in combination of two or more types.

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

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

[0310] Alternatively, the textile may be leather. The manufacturing polymer may be applied to the leather from an aqueous solution or emulsion at various stages of leather processing, for example, during the wet processing of the leather or during the finishing of the leather, to render the leather hydrophobic and oleophobic. Alternatively, the textile may be paper. The manufacturing polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example, during the drying of the paper.

[0311] "Treatment" means applying the water repellent composition to a substrate by immersion, spraying, coating, or the like. The treatment allows the fluorine-free copolymer (A) and the isocyanate derivative (B), which are active ingredients of the water repellent composition, to penetrate into the interior of the substrate and / or adhere to the surface of the substrate. In other words, the treatment provides a substrate (e.g., a textile product) to which the fluorine-free copolymer (A) and the isocyanate derivative (B) in the water repellent composition of the present disclosure are adhered.

[0312] [Pretreatment of Textile Products] The textile product may be pretreated before being treated with the water repellent composition of the present disclosure. Pretreatment of the textile product can impart excellent fastness to the textile product after treatment with the water repellent composition.

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

[0314] The method for pretreating a textile product is not limited, and the textile product can be pretreated by a conventionally known method. The pretreatment liquid may be dispersed and diluted in an organic solvent or water as necessary, and applied to the surface of the textile product by a known method such as dip coating, spray coating, foam coating, etc., followed by drying. The pH and temperature of the pretreatment liquid may be adjusted depending on the desired degree of treatment. As an example of a method for pretreating a textile product, a method for pretreating a textile product with a hydrocarbon-based water repellent will be described in detail.

[0315] The pretreatment method for textile products is to add -SO ３ M １ (In the formula, M １ represents a monovalent cation), ２ (In the formula, M ２ represents a monovalent cation), and —O—P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) (hereinafter, also referred to as a "specific functional group").

[0316] M １ Examples of M include H, K, Na, and ammonium ions which may have a substituent. ２ Examples of X include H, K, Na, and ammonium ions which may have a substituent. １ or X ２ When is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0317] Fibers containing the specific functional groups (hereinafter sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following methods: (i) A compound having the specific functional groups is attached to a fiber material. The attachment of the compound may be in a state where a portion of the compound is chemically bonded to a portion of the fiber, to the extent that a sufficient amount of the specific functional groups remains. (ii) Fibers are prepared in which the specific functional groups are directly introduced into the material that constitutes the fiber.

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

[0319] The raw material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The form of the fiber material may be any of fibers (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, paper, etc.

[0320] In this embodiment, from the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use a textile material containing polyamide and polyester as raw materials, and it is particularly preferable to use nylons such as nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate and polylactic acid, and mixed fibers containing these.

[0321] Above -SO ３ M １ A phenolic polymer can be used as the compound having the formula:

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

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

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

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

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

[0326] The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

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

[0328] As the polycarboxylic acid polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer, or a commercially available product can be used.

[0329] Examples of methods for producing polycarboxylic acid polymers include adding a radical polymerization initiator to an aqueous solution of the above-mentioned monomer and / or its salt and heating the mixture at 30 to 150°C for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, or isopropyl alcohol, or an aqueous solvent such as acetone, may be added to the aqueous solution of the above-mentioned monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; redox-based polymerization initiators such as combinations of persulfates and sodium bisulfite; hydrogen peroxide; and water-soluble azo-based polymerization initiators. These radical polymerization initiators may be used alone or in combination. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.

[0330] In addition to the above-mentioned monomers, copolymerizable monomers can be used for radical polymerization. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. Preferred acrylates and methacrylates have a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used alone or in combination of two or more.

[0331] The carboxyl group in the polycarboxylic acid polymer may be free or may be neutralized with an alkali metal, an amine compound, etc. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

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

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

[0334] The above -O-P(O)(OX １ ) (OX ２ ) may be exemplified by phosphate ester compounds represented by the following general formula: [In the formula, X １ or X ２ is as defined above, and X ３ represents an alkyl group having 1 to 22 carbon atoms.

[0335] As the phosphate ester compound, phosphate monoesters, diesters and triesters, in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

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

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

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

[0339] Methods for treating textile materials with the pretreatment liquid include, for example, padding, immersion, spraying, and coating. Examples of padding include methods using padding devices described on pages 396-397 of "Textile Dyeing and Processing Dictionary" (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of "Color Dyeing Chemistry III" (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating include methods using coating machines described on pages 473-477 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of immersion include methods using batch dyeing machines described on pages 196-247 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). These machines include jet dyeing machines, air jet dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, and cheese dyeing machines. Examples of spray treatment include air spraying, in which the treatment liquid is atomized using compressed air, and methods using a hydraulic atomization air spray. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be adjusted appropriately, taking into account various conditions, such as the purpose and performance. Furthermore, when the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after application to remove the water. The drying method is not particularly limited, and may be either a dry heat method or a wet heat method. The drying temperature is also not particularly limited, and may be, for example, drying at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment at a temperature of 100 to 180°C for 10 seconds to 5 minutes may be performed after drying.

[0340] When the textile material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as the dyeing. However, when reduction soaping is carried out, there is a risk that the compound having the specific functional group (e.g., a phenolic polymer compound) adsorbed during the treatment may fall off, so it is preferable to carry out the treatment after reduction soaping after dyeing.

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

[0342] In the functional group introduction step using a pretreatment liquid, the amount of the compound having the specific functional group attached is preferably 1.0 to 7.0 parts by weight per 100 parts by weight of the textile material. Within this range, durable water repellency and texture can both be achieved at high levels.

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

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

[0345] In the functional group introduction step using a pretreatment liquid, it is preferable to remove the compound having the specific functional group that has been treated in excess. An example of a removal method is washing with water. By performing sufficient removal, it is possible to prevent the development of water repellency in the subsequent water repellent treatment from being hindered, and in addition, the feel of the resulting textile product is improved. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fiber before contacting it with a hydrocarbon-based water repellent.

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

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

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

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

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

[0351] 100 No wetting or water droplets were observed on the surface. 90 No wetting on the surface, but small water droplets were observed. 80 Small individual water droplets were observed on the surface. 70 Wetting was observed on half of the surface, with small individual wettings penetrating the fabric. 50 Wetting was observed on the entire surface. 0 Wetting was observed on both the front and back surfaces.

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

[0353] [Preparation of Raw Materials] (Production Example of Acrylic Polymer-Containing Aqueous Dispersion) Production Example 1: A 500 ml plastic container was charged with 30 g of a water-soluble glycol solvent as an organic solvent, 120 g of pure water as a liquid medium, 58.2 g of stearyl acrylate as a long-chain aliphatic hydrocarbon group-containing (meth)acrylate, 2 g of sorbitan fatty acid ester as a surfactant, 0.1 g of acetic acid as an organic acid, 2 g of a cationic emulsifier, and 6 g of polyoxyethylene alkyl ether. The mixture was heated to 80 ° C., stirred at 2000 rpm with a homomixer for 1 minute, and then ultrasonically emulsified and dispersed for 15 minutes. Next, this mixture was transferred to a 500 ml autoclave, and after nitrogen substitution, 0.2 g of lauryl mercaptan as a chain transfer agent and 1.8 g of vinyl chloride as a copolymerizable monomer were charged. Furthermore, 1 g of an azo group-containing water-soluble initiator was added as a polymerization initiator, and the mixture was heated to 60 ° C. and reacted for 4 hours to obtain an aqueous dispersion of an acrylic polymer (hydrocarbon-based water-repellent resin). This dispersion was further diluted with pure water to prepare an aqueous dispersion of a hydrocarbon-based water-repellent resin with a solids concentration of 30% (more specifically, an aqueous dispersion containing a hydrocarbon-based water-repellent resin, a surfactant, and a liquid medium).

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

[0355]

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

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

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

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

[0360] (Production Examples of Silicone-Containing Aqueous Dispersions) Production Example 11 Methyl hydrogen silicone oil (SiH:SiCH as measured by 1H NMR) was placed in a 200 mL four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser. ３ 12 g of 1-hexacosene (molar ratio = 50:50) and 0.02 g of platinum catalyst were charged. Next, 36 g of 1-hexacosene was charged into the dropping funnel, and while maintaining the temperature at 70°C, 1-hexacosene was added dropwise from the dropping funnel. After completion of the dropwise addition, the reaction was further carried out at 70°C for 3 hours. The disappearance of the SiH peak was confirmed by infrared spectroscopy (IR), yielding 47 g of solid silicone polymer. Next, 28 g of silicone polymer, 5.6 g of water-soluble glycol solvent, 60 g of pure water, 1.7 g of sorbitan fatty acid ester, 0.7 g of polyoxyethylene alkyl ether, and 0.6 g of cationic emulsifier were charged into a 250 ml glass container, heated to 75°C, stirred at 2000 rpm with a homomixer for 1 minute, and then ultrasonically emulsified and dispersed for 10 minutes to obtain an aqueous dispersion of the silicone polymer. Pure water was then added to prepare an aqueous dispersion of the silicone polymer with a solids concentration of 30 wt%.

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

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

[0363] [Examples 1 to 11, Comparative Examples 1 to 4] The above-described aqueous dispersion and hydrophilic particles (average temporary particle size 25 nm, zeta potential +45 mV, turbidity 2.0 ppm) shown in Table 2 were added and mixed to obtain aqueous dispersions with a solids concentration of 30% in accordance with the composition weight ratio shown in Table 2. This aqueous dispersion was diluted with tap water to prepare 1,000 g of a test liquid with a solids concentration of 1.0 wt %. Next, test cloths (polyester fabric, nylon fabric) were impregnated with this test liquid and passed through a mangle. The test cloths were passed through a pin tenter at 160°C for 1 minute, dried, cured, and then subjected to the above-described tests.

[0364] Example 12 The above-described aqueous dispersion was mixed with the antibacterial and antifungal agent shown in Table 2 (75 ppm of benzisothiazolin-3-one, and 75 ppm of a mixture of 5-chloro-2-methyl-2H-isothiazol-3-one and 2-methyl-2H-isothiazol-3-one (weight ratio 3:1)) to obtain an aqueous dispersion having a solids concentration of 30% in accordance with the composition weight ratio shown in Table 2. This aqueous dispersion was diluted with tap water to prepare 1,000 g of a test liquid having a solids concentration of 1.0 wt %. Next, test cloths (polyester fabric, nylon fabric) were impregnated with this test liquid and passed through a mangle. The test cloths were passed through a pin tenter at 160°C for 1 minute, dried, cured, and then subjected to the above-described tests.

[0365]

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

Claims

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

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

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

4. The water repellent composition according to any one of claims 1 to 3, which contains silicone.

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

6. The water repellent composition according to any one of claims 1 to 5, wherein in the non-fluorinated copolymer (A), the amount of repeating units derived from the monomer (a2) is 3 to 7% by weight, based on the total amount of repeating units derived from the monomer (a1) and the repeating units derived from the monomer (a2).

7. The water repellent composition according to any one of claims 1 to 6, further comprising an isocyanate derivative (B).

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

9. The water repellent composition according to claim 7 or 8, wherein the isocyanate derivative (B) is a polyurethane.

10. The water repellent composition according to any one of claims 7 to 9, wherein the amount of the isocyanate derivative (B) is 0.1 to 20 parts by mass per 100 parts by mass of the non-fluorinated copolymer (A).

11. The water repellent composition according to any one of claims 7 to 10, wherein the isocyanate derivative (B) is a compound obtained by reacting at least one active hydrogen compound selected from the group consisting of hydrocarbon alcohols, sugar alcohol modifications, and hydroxy acid modifications with at least one raw material isocyanate selected from the group consisting of acyclic aliphatic polyisocyanates and derivatives thereof.

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

13. The hydrophobic monomer (a1) is represented by the formula: CH ２ =CH-C(=O)-Y １１ -R １１ [In the formula, R １１ is an alkyl group having 12 to 25 carbon atoms; １１ is -O- or -O-(CH ２ ) m the chloride monomer (a2) is vinyl chloride, and in the non-fluorinated copolymer (A), the amount of repeating units derived from the monomer (a2) is 3 to 7% by weight based on the total amount of repeating units derived from the monomer (a1) and the repeating units derived from the monomer (a2).

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

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

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

17. -SO ３ M １ (In the formula, M １ represents a monovalent cation), ２ (In the formula, M ２ represents a monovalent cation), and １ ) (O.X. ２ ) (wherein, X １ and X ２ each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms), to which a compound having one or more functional groups selected from the group consisting of monovalent groups represented by the formula:

Images