Water-repellent composition

Abstract

To provide a water repellent composition capable of imparting both good water repellency and good slip resistance to a fiber product.SOLUTION: The water repellent composition contains: a non-fluorine copolymer (A) which has a repeating unit derived from a hydrophobic monomer (a1) having a C2-40 hydrocarbon group, and a repeating unit derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride; and an isocyanate derivative (B). In the non-fluorine copolymer (A), the amount of the repeating unit derived from the monomer (a2) is 1-15 wt.% based on the total of the amount of the repeating unit derived from the monomer (a1) and the amount of the repeating unit derived from the monomer (a2).SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] As a water-repellent agent for imparting water-repellency to a base material (especially a fiber product), the development of a non-fluorine-based water-repellent agent has been promoted.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] When a conventional water-repellent agent is used for a fiber product, there is a risk that the seams will slip off (that is, slip), resulting in a decrease in the reliability of the fiber product.

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

Means for Solving the Problems

[0006] The present disclosure includes the following aspects: [Item 1] A non-fluorine copolymer (A) containing a repeating unit derived from a hydrophobic monomer (a1) having a hydrocarbon group with 2 to 40 carbon atoms, and a repeating unit derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride, and an isocyanate derivative (B), In the non-fluorine copolymer (A), the amount of the repeating unit derived from the monomer (a2) is 1 to 15% by weight based on the total amount of the repeating unit derived from the monomer (a1) and the repeating unit derived from the monomer (a2), the water-repellent composition. [Item 2] In the hydrophobic monomer (a1), the hydrocarbon group is a linear alkyl group having 10 or more carbon atoms The water-repellent composition according to Item 1, which is as described above. [Item 3] The hydrophobic monomer (a1) has the formula: CH2 = C(-R 12 )-C(=O)-Y 11 -(R 11 ) k [In the formula, R 11 is a hydrocarbon group having 2 to 40 carbon atoms, R 12 is a hydrogen atom, a monovalent organic group or a halogen atom, Y 11 is a divalent to tetravalent group composed of at least one selected from a direct bond, a divalent to tetravalent hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2- and -NR'-(R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), k is 1 to 3.] The water-repellent composition according to Item 1 or 2, which is a compound represented by the above formula. [Item 4] The isocyanate derivative (B) has an alkyl group having 12 or more and 30 or less carbon atoms, and the water-repellent composition according to any one of Items 1 to 3. [Item 5] The isocyanate derivative (B) is polyurethane, and the water-repellent composition according to any one of Items 1 to 4. [Item 6] The water repellent composition according to any one of items 1 to 5, wherein the isocyanate derivative (B) is a compound obtained by reacting at least one active hydrogen compound selected from the group consisting of hydrocarbon alcohols, sugar alcohol-modified products, and hydroxy acid-modified products with at least one raw material isocyanate selected from the group consisting of acyclic aliphatic polyisocyanates and derivatives thereof. [Item 7] The water repellent composition according to any one of items 1 to 6, which contains silicone. [Item 8] The water repellent composition according to item 7, wherein the amount of the silicone is 0.1 part by weight to 10 parts by weight per 100 parts by weight of the non-fluorinated copolymer (A). [Item 9] In the non-fluorinated copolymer (A), the amount of the repeating unit derived from the monomer (a2) is 1 to 9% by weight based on the total of the amount of the repeating unit derived from the monomer (a1) and the amount of the repeating unit derived from the monomer (a2). The water repellent composition according to any one of items 1 to 8. [Item 10] The water repellent composition according to any one of items 1 to 9, wherein the amount of the isocyanate derivative (B) is 0.1 part by weight to 10 parts by weight per 100 parts by weight of the non-fluorinated copolymer (A). [Item 11] The hydrophobic monomer (a1) has the formula: CH2=C(-R 12 )-C(=O)-Y 11 -(R 11 ) k [In the formula, R 11 is a hydrocarbon group having 2 to 40 carbon atoms, R 12 is a hydrogen atom, a monovalent organic group or a halogen atom, Y 11 is a divalent to tetravalent group composed of at least one selected from a direct bond, a divalent to tetravalent hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2- and -NR'-(R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), k is 1 to 3.] It is a compound represented by The isocyanate derivative (B) has an alkyl group having 12 to 30 carbon atoms and is a compound obtained by reacting at least one active hydrogen compound selected from the group consisting of hydrocarbon alcohols, sugar alcohol modified products, and hydroxy acid modified products with at least one raw material isocyanate selected from the group consisting of acyclic aliphatic polyisocyanates and derivatives thereof. The water repellent composition according to Item 1, wherein the amount of the isocyanate derivative (B) is 0.1 part by weight to 20 parts by weight per 100 parts by weight of the non-fluorine copolymer (A). [Item 12] The hydrophobic monomer (a1) has the formula: CH2=CH-C(=O)-Y 11 -R 11 [In the formula, R 11 is an alkyl group having 12 to 25 carbon atoms, Y 11 is -O- or -O-(CH2) m -NH-C(=O)-, m is an integer of 2 or 4. It is a compound represented by ]. The chloride monomer (a2) is vinyl chloride, The isocyanate derivative (B) is a compound obtained by reacting a hydrocarbon alcohol having an alkyl group having 12 to 25 carbon atoms with an isocyanurate derivative of an acyclic aliphatic polyisocyanate having an aliphatic hydrocarbon group having 2 to 10 carbon atoms or a compound obtained by reacting a sorbitan modified product modified with an alkyl group having 12 to 25 carbon atoms with a biuret derivative of an acyclic aliphatic polyisocyanate having an aliphatic hydrocarbon group having 2 to 10 carbon atoms, The water repellent composition according to Item 1, wherein the amount of the isocyanate derivative (B) is 1 part by weight to 10 parts by weight per 100 parts by weight of the non-fluorine copolymer (A). [Item 13] A method for manufacturing a fiber product, comprising applying the water-repellent composition according to any one of Items 1 to 12 to a fiber substrate. [Item 14] Before applying the water-repellent composition to the fiber substrate, the fiber is -SO3M 1 (wherein M 1 represents a monovalent cation) a monovalent group represented by, -COOM 2 (wherein M 2 represents a monovalent cation) a monovalent group represented by, and -O-P(O)(OX 1 )(OX 2 (wherein X 1 and X 2 each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms)) a step of imparting one or more functional groups selected from the group consisting of monovalent groups represented by, the method for manufacturing a fiber product according to Item 13. [Item 15] A fiber product to which the non-fluorine copolymer (A) and the isocyanate derivative (B) in the water-repellent composition according to any one of Items 1 to 12 are attached. [Item 16] -SO3M 1 (wherein M 1 represents a monovalent cation) a monovalent group represented by, -COOM 2 (wherein M 2 represents a monovalent cation) a monovalent group represented by, and -O-P(O)(OX 1 )(OX 2 (wherein X 1 and X 2 each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms)) a fiber product according to Item 15, to which a compound having one or more functional groups selected from the group consisting of monovalent groups represented by is attached. [Advantages of the Invention]

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

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] <Definition of Terms> As used herein, the term "n-valent group" means a group having n bonds, i.e., a group forming n bonds. Further, the term "n-valent organic group" means an n-valent group containing carbon. Such an organic group is not particularly limited, and may be a hydrocarbon group or a derivative thereof. The derivative of a hydrocarbon group means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the terminal or molecular chain of the hydrocarbon group.

[0009] As used herein, the term "hydrocarbon group" means a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but may be, for example, a C 1-20 hydrocarbon group, such as an aliphatic hydrocarbon group, an aromatic hydrocarbon group, etc. The above "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Further, 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, unless otherwise specified, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition is applied independently for each appearance, regardless of whether the expression "independently at each occurrence", "independently of each other", "independently respectively" or a similar expression is explicitly described.

[0011] The chemical structures described in this specification should be understood not to include chemical structures that are recognized by those skilled in the art as chemically impossible or extremely unstable.

[0012] <Water Repellent Composition> The water-repellent composition in the present disclosure contains a repeating unit derived from a hydrophobic monomer (a1) having a hydrocarbon group with 2 to 40 carbon atoms, and a repeating unit derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride, and an isocyanate derivative (B). The water-repellent composition in the present disclosure can adhere to a substrate (especially a textile product) and impart both good water repellency and good slip resistance to the substrate.

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

[0014] [[(A) Non-fluorine copolymer]] The non-fluorine copolymer (A) does not have a fluorine atom.

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

[0016] [[(a1) Hydrophobic monomer]] The hydrophobic monomer (a1) has one ethylenically unsaturated double bond and a hydrocarbon group with 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, preferably linear. The number of carbon atoms of the hydrocarbon group may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 11 or more, 12 or more, 14 or more, or 16 or more, preferably 6 or more. The number of carbon atoms of the hydrocarbon group may be 40 or less, 30 or less, 25 or less, 22 or less, or 20 or less, preferably 30 or less.

[0018] The hydrophobic monomer (a1) has the formula: CH2=C(-R 12 )-C(=O)-Y 11 -(R 11 ) k [wherein, R 11 is a hydrocarbon group having 2 to 40 carbon atoms, R 12 is a hydrogen atom, a monovalent organic group or a halogen atom, Y 11 is a divalent to tetravalent group composed of at least one selected from a direct bond, a hydrocarbon group having 1 carbon atom with 2 to 4 valences, -C6H4-, -O-, -C(=O)-, -S(=O)2- and -NR'-(R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), k is 1 to 3.] It may be a monomer represented by

[0019] R 11is preferably a branched or linear (preferably long-chain linear) hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The -CH3 group has a lower surface free energy and is more likely to exhibit liquid repellency than the -CH2- group. Therefore, a structure with many branches and many -CH3 groups is preferred. On the other hand, a long-chain alkyl group of a certain length exhibits high liquid repellency due to its crystallinity. Thus, it may be a branched hydrocarbon group (e.g., a branched alkyl group), particularly a t-butyl group or an isopropyl group, a multi-branched structure group, or a long-chain hydrocarbon group (or a long-chain linear hydrocarbon group), such as an alkyl group. R 11 The carbon number of 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, preferably 10 or more. R 11 The carbon number of R may be 40 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 12 or less.

[0020] k is 1, 2, or 3. When Y 11 has a tetravalent hydrocarbon group with 1 carbon atom, etc., k = 3. Y 11 When Y has a trivalent hydrocarbon group with 1 carbon atom, etc., k = 2. Y 11 When Y does not have a trivalent and tetravalent hydrocarbon group with 1 carbon atom (e.g., when Y 11 has a divalent hydrocarbon group with 1 carbon atom (-CH2-) (e.g., 1 to 6), k = 1.

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

[0022] Y 11 is preferably a divalent group. Examples of the C1 hydrocarbon group having 2 to 4 valences are -CH2-, -CH= having a branched structure, and -C≡ having a branched structure.

[0023] Y 11 is -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’ is independently a direct bond, -O-, -NR’- (R’ is a hydrogen atom or a C1-4 hydrocarbon group), or -S(=O)2-, X’ is -(CH2) m -(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l -(l is independently an integer of 0 to 5, and -C6H4- is a phenylene group).] may be. Y 11 is preferably not only a divalent hydrocarbon group.

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

[0025] Y 11 is -O-, -NH-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m-O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -NH-C(=O)-NH- [In the formula, m is an integer of 1 to 5, particularly 2 or 4.] It is preferable that Y 11 is -O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, or -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, particularly -O-(CH2) m It is more preferable that it is -NH-C(=O)-.

[0026] Y 11 is -O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, or -O-(CH2) m -NH-C(=O)- [In the formula, m is an integer of 1 to 5, particularly 2 or 4.] is even more preferable.

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

[0028] The hydrophobic monomer (a1) preferably has no reactive group or hydrophilic group. Examples of the reactive group are an epoxy group, a chloromethyl group, a bromomethyl group, an iodomethyl group, an isocyanate group, and a blocked isocyanate group. Examples of the hydrophilic group are a hydroxyl group, a polyalkylene oxide group, an amino group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an alkali metal or alkaline earth metal salt of carboxylic acid, sulfonic acid, or phosphoric acid, chlorine or bromine, an ammonium base having an iodine ion as a counter anion, 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 the hydrophobic monomer (a1) may be 75° or more, 80° or more, 85° or more, 90° or more, 95° or more, 100° or more, 101° or more, 103° or more, 105° or more, 110° or more, 115° or more, or 120° or more, preferably 90° or more, or 100° or more. The water contact angle of the homopolymer of the hydrophobic monomer (a1) may be 160° or less, 150° or less, 140° or less, 130° or less, 125° or less, or 110° or less. It is preferable that the water contact angle is within the above range from the viewpoints of the liquid repellency, particularly water repellency, of the copolymer, etc. The water contact angle of the homopolymer may be a value obtained by spin-coating a chloroform solution with a solid content concentration of 1.0% of the homopolymer on a silicon wafer substrate, dropping 2 μL of water onto the coating film, and measuring the contact angle 1 second after the droplet adheres.

[0031] Specific examples of the hydrophobic monomer (a1) are as follows. The compounds of the following chemical formulas are acrylic compounds in which the α-position is a hydrogen atom, but may be methacrylic compounds in which the α-position is a methyl group and α-chloroacrylic compounds in which the α-position is a chlorine atom. CH2=CHC(=O)OC 18 H 37 CH2=CHC(=O)OC n H 2n+1 CH2=CHC(=O)OC2H4OC(=O)NHC 18 H 37 CH2=CHC(=O)OC2H4NHC(=O)OC 18 H 37 CH2=CHC(=O)OC mH 2m NHC(=O)C n H 2n+1 CH2=CHC(=O)OC2H4OC(=O)NHC n H 2n+1 CH2=CHC(=O)OC2H4NHC(=O)OC n H 2n+1 CH2=CHC(=O)OC2H4NHC(=O)NHC n H 2n+1 CH2=CHC(=O)OC4H8OC(=O)NHC n H 2n+1 CH2=CHC(=O)NHC m H 2m OC(=O)NHC n H 2n+1 [Chemical formula] [Chemical formula] CH2=CHC(=O)OC m H 2m NHSO2C n H 2n+1 CH2=CHC(=O)OC m H 2m SO2NHC n H 2n+1 [In the above formula, n is a number from 3 to 40, and m is a number from 1 to 5.] [Chemical formula]

[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, stearic acid amidoethyl (meth)acrylate, 2-stearamidoethyl acrylate, CH2=CHC(=O)OC2H4NHSO2C 18 H 37 and the like. These may be used alone or in combination of two or more.

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

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

[0035] ((a3) cyclic hydrocarbon group-containing monomer) The non-fluorine 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, and is preferably aliphatic. The cyclic hydrocarbon group may be saturated or unsaturated, and is preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged cyclic group, and a bridged cyclic group is preferred. The cyclic hydrocarbon group may have a chain group (for example, a linear or branched hydrocarbon group).

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

[0039] Specific examples of the cyclic hydrocarbon group include cyclohexyl group, t-butylcyclohexyl group, adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, bornyl group, isobornyl group, norbornyl group, dicyclopentanyl group, dicyclopentenyl group, benzyl group, phenyl group, naphthyl group, 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (for example, cyclohexylene group, adamantylene group, phenylene group, naphthylene group, etc.) and groups which are substituents 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 obtained by substituting these acrylates with acrylamide. These may be used alone or in combination of two or more.

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

[0042] The crosslinkable monomer (a4) preferably has a (meth)acryl group as an 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), etc.

[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-acetoxyacetoxyethyl (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, compounds obtained by substituting these acrylates with acrylamide, etc. These may be used alone or in combination of two or more. These may be used alone or in combination of two or more.

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

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

[0047] (Composition of the polymer) The amount of the repeating unit 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 with respect to the non-fluorine copolymer (A). The amount of the repeating unit 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 with respect to the non-fluorine copolymer (A).

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

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

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

[0051] In the non-fluorine copolymer (A), the amount of the repeating unit derived from the chloride monomer (a2) may be 15% by weight or less, 13% by weight or less, 11% by weight or less, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, or 5% by weight or less, preferably 10% by weight or less, more preferably 7% by weight or less, based on the total of the amount of the repeating unit derived from the hydrophobic monomer (a1) and the amount of the repeating unit derived from the chloride monomer (a2).

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

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

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

[0055] The amount of the repeating unit 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 with respect to 100 parts by weight of the repeating unit derived from the hydrophobic monomer (a1). The amount of the repeating unit 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 with respect to 100 parts by weight of the repeating unit derived from the hydrophobic monomer (a1).

[0056] The amount of the repeating unit 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 with respect to 100 parts by weight of the repeating unit derived from the hydrophobic monomer (a1). The amount of the repeating unit 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 with respect to 100 parts by weight of the repeating unit derived from the hydrophobic monomer (a1).

[0057] The amount of the repeating unit 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 with respect to 100 parts by weight of the repeating unit derived from the hydrophobic monomer (a1). The amount of the repeating unit 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 with respect to 100 parts by weight of the repeating unit derived from the hydrophobic monomer (a1).

[0058] The amount of the repeating unit 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 with respect to 100 parts by weight of the repeating unit derived from the hydrophobic monomer (a1). The amount of the repeating unit 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 with respect to 100 parts by weight of the repeating unit derived from the hydrophobic monomer (a1).

[0059] [(B) Isocyanate Derivative] The isocyanate derivative (B) is a compound obtained by the reaction of an active hydrogen compound and a raw material isocyanate, and has a portion derived from the active hydrogen-containing compound and a portion derived from the raw material isocyanate. Note that the isocyanate derivative (B) is different from an isocyanate-based curing agent and usually does not have an isocyanate group.

[0060] The isocyanate derivative (B) has -NHCO- formed by the reaction of an active hydrogen compound and a raw material isocyanate (where -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) and an active hydrogen-reactive group (typically an isocyanate group) of the compound (b). The isocyanate derivative (B) is typically a urethane (especially a polyurethane).

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

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

[0064] The water contact angle of the isocyanate derivative (B) may be 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, 100° or more, or 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. By having a water contact angle of the isocyanate derivative (B) of the above lower limit or more, excellent water repellency can be imparted to the substrate. The water contact angle refers to the static contact angle with respect to the spin-coated film of the isocyanate derivative (B), and it means the value obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the droplet adheres.

[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 typically it is a hydroxy group.

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

[0068] The hydrocarbon group in the hydrocarbon alcohol (α1) may be the hydrocarbon group having 6 or more and 40 or less carbon atoms described above, and the above description is incorporated. The hydrocarbon group in the hydrocarbon alcohol (α1) may preferably be the alkyl group having 12 or more and 30 or less carbon atoms described above, and the above description is incorporated.

[0069] Also, the hydrocarbon alcohol (α1) preferably has 1 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, eicosanol; branched saturated hydrocarbon group-containing alcohols such as isomyristyl alcohol, isocetyl alcohol, isostearyl alcohol, isoeicosyl alcohol; linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, icosenyl alcohol, docosenyl alcohol, tetracosenyl alcohol, hexacosenyl alcohol, octacosenyl alcohol; and branched unsaturated hydrocarbon group-containing active hydrogen compounds such as phytol.

[0071] Here, the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol may be used in combination. When the linear saturated hydrocarbon group-containing alcohol and the 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, based on 100 parts by weight of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. Also, 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, based on 100 parts by weight of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. If the blending ratio of the linear saturated hydrocarbon group-containing alcohol is at least the above lower limit, the crystallinity of the hydrocarbon group is improved, and as a result, the water repellency of the water-repellent treated article treated with this water repellent composition can be improved.

[0072] [(α2) Sugar alcohol / hydroxy acid modified product] The active hydrogen compound may be a sugar alcohol / hydroxy acid modified product (α2) which is a sugar alcohol / hydroxy acid (sugar alcohol and / or hydroxy acid) modified with a hydrocarbon group having 6 to 40 carbon atoms. The types of sugar alcohol / hydroxy acid are not limited and may be cyclic or acyclic. Examples of sugar alcohols include monosaccharides, reducing sugars, amino sugars, aldonic acids, aldonic acid lactones, and examples of hydroxy acids include hydroxy polycarboxylic acids and the like. The sugar alcohol / hydroxy acid may be a substance present in vivo. Examples of sugar alcohol / hydroxy acid include aldoses and ketoses, for example, compounds derived from tetrose, pentose, hexose, and heptose, but are not limited thereto. 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, talopyranose, allopyranose, altropyranose, idopyranose, glucopyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fucitol, iditol, inositol, pentaerythritol, dipentaerythritol, volemitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, citric acid, gluconic acid lactone, glyceric acid lactone, xylonic acid lactone, glucosamine, galactosamine, or mixtures thereof. The carbon number of the sugar alcohol / hydroxy acid may be 2 or more, 4 or more, or 6 or more, and may be 30 or less, 20 or less, or 10 or less. The average OH value of the compound (α2) may be in the range of more than 0 to about 230, preferably about 10 to about 175, and most preferably about 25 to about 140.

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

[0074] In the sugar alcohol / hydroxy acid modified product (α2), at least one active hydrogen (for example, the hydrogen in the OH group or carboxyl group) of the sugar alcohol and / or hydroxy acid is -R α2 , -C(O)R α2 , -(CH2CH2O) n (CH(CH3)CH2O) m R α2 , -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 , or may be substituted with an active hydrogen substituent selected from these mixtures. Here, R α2 is a hydrogen atom or a hydrocarbon group having 6 or more and 40 or less carbon atoms, each n is independently 0 to 20, each m is independently 0 to 20, and m + n may be greater than 0. Note that the compound (α2) has at least one active hydrogen. For example, in the sugar alcohol / hydroxy acid modified product, at least one (1 or 2 or more) of the active hydrogens of the sugar alcohol / hydroxy acid may be unmodified, and the active hydrogen (for example, -OH group) may react with the active hydrogen reactive group (especially isocyanate group) of the compound (b) to form -NHCO-. Note that the number of carbon atoms of 6 or more and 40 or less in the sugar alcohol / hydroxy acid modified product (α2) may preferably be the above-described alkyl group having 12 or more and 30 or less carbon atoms, and the above description is incorporated by reference.

[0075] ((α21) Sorbitan modifier) The sugar alcohol / hydroxy acid modifier (α2) may be a sorbitan modifier (α21) in which sorbitan is modified with a hydrocarbon group having 6 to 40 carbon atoms, particularly may be alkyl sorbitan, and sorbitan 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 a compound substituted with these mixtures (where R α2 is a hydrocarbon group having 6 to 40 carbon atoms). For example, it may be a compound in which sorbitan is mono-substituted, di-substituted, or tri-substituted with -C(O)R α2 . Here, sorbitan may contain an amount of sorbitol, isosorbide, or other intermediates or by-products. The hydrocarbon group in the sorbitan modifier (α21) may be the above-described hydrocarbon group having 6 to 40 carbon atoms, and the above description is incorporated by reference. The sorbitan modifier (α21) may have an alkyl group having 12 to 30 carbon atoms. For the alkyl group having 12 to 30 carbon atoms, the above description is incorporated by reference. Commercially available sorbitans such as SPAN can be used as the above alkyl sorbitan.

[0076] In one aspect, at least one active hydrogen substituent may be -C(O)R α2 , where R α2 may be a linear or branched 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-substituted, di-substituted, and tri-substituted sorbitans derived from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and mixtures thereof. Particularly preferred compounds include mono-substituted, di-substituted, and tri-substituted sorbitan stearate, or sorbitan behenate.

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

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

[0079] ((α22) Citric acid modifier) The sugar alcohol / hydroxy acid modifier (α2) may be a citric acid modifier (α22) in which a hydrocarbon group having 6 to 40 carbon atoms is modified to citric acid, and may particularly be an alkyl citrate. For example, the citric acid modifier (α22) may exist as a monosubstituted, disubstituted, or trisubstituted product having an alkyl group. The hydrocarbon group in the citric acid modifier (α22) may be the hydrocarbon group having 6 to 40 carbon atoms described above, and the above description is incorporated by reference. The citric acid modifier (α22) may have an alkyl group having 12 to 30 carbon atoms. For the alkyl group having 12 to 30 carbon atoms, the above description is incorporated by reference. A mixture of citrates having various values of active hydrogen substituents may be used, and may also include a mixture of a compound having a hydrocarbon group in which R α2 has at least one unsaturated bond and a compound in which R α2 is a completely saturated hydrocarbon. The citric acid modifier (α22) may have an active hydrogen substituent selected from -(CH2CH2O) n (CH(CH3)CH2O) m R α2 or -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 (where R α2 is a hydrocarbon group having 6 to 40 carbon atoms). Examples of the citric acid modifier (α22) include, but are not limited to, trialkyl citrate.

[0080] ((α23) pentaerythritol modified product) The sugar alcohol / hydroxy acid modified product (α21) may be a pentaerythritol modified product (α23) in which a hydrocarbon group having 6 or more and 40 or less carbon atoms is modified on pentaerythritol, and may be a monosubstituted product, disubstituted product, or trisubstituted product having a hydrocarbon group having 6 or more and 40 or less carbon atoms (particularly an alkyl group), for example, dipentaerythritol ester. The active hydrogen substituent may contain -CH2C[CH2OR α2 3 (wherein R α2 is a hydrocarbon group having 6 or more and 40 or less carbon atoms). Further, the pentaerythritol modified product (α23) may be a compound having a mixture of hydrocarbon groups with different chain lengths, or a mixture of a compound in which R α2 contains at least one unsaturated bond and a compound in which R α2 is completely saturated. The hydrocarbon group in the pentaerythritol modified product (α23) may be the above-described hydrocarbon group having 6 or more and 40 or less carbon atoms, and the above description is incorporated by reference. The pentaerythritol modified product (α23) may have an alkyl group having 12 or more and 30 or less carbon atoms. For the alkyl group having 12 or more and 30 or less carbon atoms, the above description is incorporated by reference.

[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] Further, the cationic active hydrogen compound (α3) preferably has 2 or more hydroxy groups per molecule.

[0083] Examples of the cationic group include a tertiary amino group.

[0084] That is, the cationic active hydrogen compound (α3) preferably has 2 or more hydroxyl groups per molecule as the active hydrogen group and a tertiary amino group as the cationic group.

[0085] According to such a cationic active hydrogen compound, good dispersibility in a liquid medium (such as water) can be imparted, and a cationic group having an affinity for a fiber product (described later) can be introduced into the resin, so that the washing durability can be improved.

[0086] More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as the active hydrogen group 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. Preferably, N-methyldiethanolamine is mentioned.

[0088] The cationic active hydrogen compound (or the part derived from the cationic active hydrogen compound in the non-fluorine copolymer) 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 are mentioned. More preferably, acetic acid is mentioned. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, etc. Preferably, hydrochloric acid is mentioned. The acid compound is preferably an organic acid. If the acid compound contains an organic acid, the water repellency of the water repellent-treated product treated with this water repellent composition can be improved by the volatilization of the acid by heat treatment. In addition, from the viewpoint that the cationic group is easily adsorbed on the fiber product due to the volatilization of the acid by heat treatment, the washing durability for the fiber product can be improved. [(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) has the formula R α41 -X α41 [wherein In the formula, R α41 is C1-C which may contain at least one unsaturated group 30 linear or branched alkyl, hydroxy-functional C1-C 30 linear or branched alkyl, hydroxy-functional linear or branched C1-C 30 polyether, hydroxy-functional linear or branched polyester, hydroxy-functional linear or branched organosiloxane, thiol-functional C1-C 30 linear or branched alkyl, amine-functional C1-C 30 linear or branched alkyl, Y - R α411 R α412 R α413 N + -R α414 -(where Y is a halide ion, for example Cl - is. ), HOS(=O)2-R α414 -, or R α411 R α412 C=N-(where R α411 , R α412 , R α413 are each independently -H, C1-C6 alkyl, and R α414 is a divalent alkyl group having 1 to 20 carbon atoms. ). And X α41 is an isocyanate-reactive functional group such as -OH, -C(O)OH, -SH, -NH(R’), -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CH2CH2O) s (CH(CH3)CH2O) t -H, etc. (where R ’ is -H or a monovalent organic group, s is an integer from 0 to 50, t is an integer from 0 to 50, and s + t is greater than 0). ]. It may be a compound (α41) represented by

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

[0092] In one embodiment, X α41 is -OH, -C(O)OH, -SH, -NH(R ’ ), where R α41 is optionally a C1-C 30 linear or branched alkyl containing at least one unsaturated group, a hydroxy-functional C1-C 30 linear or branched alkyl, a hydroxy-functional linear or branched C1-C 30 polyether, a hydroxy-functional linear or branched polyester, a hydroxy- or amine-functional linear or branched organosiloxane, a thiol-functional C1-C 30 linear or branched alkyl, or an amine-functional C1-C 30 linear or branched alkyl.

[0093] X α41 may be -OH, and examples of such compounds (α41) include alkyl alcohols such as propanol and butanol, or aliphatic alcohols including stearyl alcohol (R α41 is optionally a C1-C 30(which is a linear or branched alkyl), an alkyldiol or polyol such as ethanediol, propanediol, butanediol or hexanediol (R α41 is a hydroxy-functional C1-C 30 (which is a linear or branched alkyl), an alkylene glycol ether such as triethylene glycol, tetraethylene glycol, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), or a glycol ether having a mixture of PEG, PPG or THF units (R α41 is a hydroxy-functional linear or branched C1-C 30 (which is a polyether), a polyester polyol (R α41 is a hydroxy-functional linear or branched polyester), a silicone prepolymer polyol (R α41 is a hydroxy-functional linear or branched organosiloxane), N,N-dimethylaminoethanol (R α41 is an amine-functional C1-C 30 (which is a linear or branched alkyl), choline chloride or betaine HCl (R α41 is Y - R α411 R α412 R α413 N + -R α414 (which is -), butanone oxime (R α41 is R α411 R α412 C=N-). Examples include, but are not limited to, these. The polyether polyol can contain only EO groups, only PO groups, only THF groups, or a mixture of these. Also, these polyethers can exist as block copolymers such as those specified by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). The polyether glycol preferably has an average molecular weight of about 200 or more, most preferably 350-2000.

[0094] X α41may be -C(O)OH, and examples of such compounds (α41) include fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, linoleic acid, arachidonic acid, oleic acid, or erucic acid (R α41 is a C1-C optionally containing at least one unsaturated group 30 which is a linear or branched alkyl), hydroxy-containing acids such as hydroxycaprylic acid, hydroxycapric acid, hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyarachidic acid, hydroxybehenic acid, hydroxylignoceric acid, hydroxypalmitoleic acid, hydroxylinoleic acid, hydroxyarachidonic acid, hydroxyoleic acid, or hydroxyerucic acid (R α41 is a hydroxy-functional C1-C 30 which is a linear or branched alkyl), and mercaptoalkanoic acids such as mercaptopropionic acid (R α41 is a thiol-functional C1-C 30 which is a linear or branched alkyl), but are not limited thereto.

[0095] X α41 may be -SH, and examples of such compounds (α41) include alkylthiols such as lauryl mercaptan or dodecyl mercaptan (R α41 is a C1-C optionally containing at least one unsaturated group 30 which is a linear or branched alkyl), but are not limited thereto.

[0096] X α41 may be -NH(R’), and examples of such compounds (α41) include alkylamines such as diisopropylamine, propylamine, hexylamine, or laurylamine (R α41 is a C1-C optionally containing at least one unsaturated group 30 which is a linear or branched alkyl), alkanolamines such as ethanolamine or propanolamine (R α41is a hydroxy-functional C1-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 C1-C 30 linear or branched alkyl), and aminoalkanesulfonic acids such as 2-aminoethanesulfonic acid (R α41 is HO-S(O)2R α414 -). These are examples, but not limited to these.

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

[0098] Compound (α42) may be a compound generally called 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 (e.g., two) functional groups containing active hydrogen in the molecule. As the chain extender, known chain extenders can be used, and examples thereof include aliphatic or aromatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, cyclohexanedimethanol; aliphatic or aromatic diamines or polyamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, diethyltoluenediamine; phenolic hydroxyl group-containing compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol, and o,o'-diallyl-bisphenol A; and alcoholamines such as aminoethyl ethanolamine, aminopropyl ethanolamine, aminohexyl ethanolamine, aminoethyl propanolamine, aminopropyl propanolamine, and aminohexyl propanolamine.

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

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

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

[0103] An aromatic polyisocyanate is a compound having an aromatic ring and an isocyanate group. The aromatic ring(s) possessed by the aromatic polyisocyanate may be one or more, two or more, or three or more, and may also be five or less, four or less, or three or less.

[0104] An acyclic aliphatic polyisocyanate is an aliphatic polyisocyanate having no ring structure. The acyclic aliphatic polyisocyanate may have an aliphatic hydrocarbon group having 2 to 20 carbon atoms. The aliphatic hydrocarbon group having 2 to 20 carbon atoms may be a divalent aliphatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group may be 2 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, or 14 or more, preferably 4 or more, 6 or more, or 8 or more. The number of carbon atoms of the aliphatic hydrocarbon group may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, or 10 or less, 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] A cyclic alicyclic polyisocyanate is an aliphatic polyisocyanate having a ring structure. The cyclic alicyclic polyisocyanate has an alicyclic ring that is not an aromatic ring. The cyclic alicyclic polyisocyanate may have an aliphatic hydrocarbon group having 2 to 20 carbon atoms. The aliphatic hydrocarbon group having 2 to 20 carbon atoms incorporates the description in the above acyclic aliphatic polyisocyanate.

[0106] A bridged alicyclic polyisocyanate is a polycyclic compound having a bridging structure by a methylene group or the like in the ring structure. The bridged alicyclic polyisocyanate may have an aliphatic hydrocarbon group having 2 to 20 carbon atoms. The aliphatic hydrocarbon group having 2 to 20 carbon atoms incorporates the description in the above acyclic aliphatic polyisocyanate.

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

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

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

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

[0111] Examples of the raw material isocyanate include aromatic polyisocyanates selected from 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), tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(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-diisocyanatomethyl caproate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate; Cycloaliphatic polyisocyanates selected from 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), methylene bis(cyclohexyl isocyanate (4,4’-, 2,4’- or 2,2’-methylene bis(cyclohexyl isocyanate or mixtures thereof) (hydrogenated MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI); Bridged cycloaliphatic polyisocyanates selected from norbornene diisocyanate, norbornane diisocyanatomethyl, bicycloheptane triisocyanate, diisocyanatomethyl bicycloheptane, di(diisocyanatomethyl)tricyclodecane; [Chemical] [Chemical] a compound selected from and the above isocyanate biuret modified product, polymers of polyisocyanates (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), allophanate derivatives (e.g., allophanate derivatives produced from the reaction of the above polyisocyanate with a monohydric alcohol or a dihydric alcohol, etc.), polyol derivatives (e.g., polyol derivatives (alcohol adducts, preferably trimethylolpropane adducts) produced from the reaction of the above polyisocyanate with a trihydric alcohol (e.g., trimethylolpropane, etc.)), biuret derivatives (e.g., biuret derivatives produced from the reaction of the above polyisocyanate with water or amines, etc.), urea derivatives (e.g., urea derivatives produced from the reaction of the above polyisocyanate with diamines, etc.), oxadiazinetrione derivatives (e.g., oxadiazinetrione produced from the reaction of the above polyisocyanate with carbon dioxide gas, etc.), carbodiimide derivatives (carbodiimide derivatives produced from the decarboxylation condensation reaction of the above polyisocyanate, etc.), uretdione derivatives, uretonimine derivatives, etc.

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

[0113]

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

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

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

[0117] ​​The amount of the moiety derived from the sugar alcohol / hydroxy acid modifier (α2) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more based on the moiety derived from the active hydrogen compound. The amount of the moiety derived from the sugar alcohol / hydroxy acid modifier 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 moiety derived from the active hydrogen compound.

[0118] The amount of the moiety 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 moiety derived from the active hydrogen compound. The amount of the moiety 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 moiety derived from the active hydrogen compound.

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

[0120] The amount of the moiety derived from the starting 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 material isocyanate may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less with respect to the isocyanate derivative (B).

[0121] [(B) Amount of the isocyanate derivative] 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-fluorine 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 with respect to 100 parts by weight of the non-fluorine copolymer (A).

[0122] [Silicone] Preferably, the water-repellent composition in the present disclosure contains silicone in addition to the hydrophobic monomer (a1). By containing silicone, it is possible to have good water repellency and slip resistance at the same time.

[0123] The silicone has the formula:[[]] (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )2-O-] b -Si(R 53 )3(S1) [wherein each of R 51 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, each of R 53 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.] and may be a polymer represented by this.

[0124] R 51 and R 53 In the formulae, the alkyl group having 1 to 40 carbon atoms and the aryl group having 6 to 40 carbon atoms may be unsubstituted or may be substituted. R 51 and R 53 Specific examples of R and 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 are substituted with a halogen atom, an amino group, a cyano group, etc. 51 and R 53 are preferably a methyl group or an ethyl group. R 51 and R 53 In the formulae, 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 are 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, at least one of R in formula (S1), at least one of R, or at least one of each of R and R may be a long-chain hydrocarbon group, 51 R 53 R 51 and R 53 R 51At least one (e.g., one) of them may be a long-chain hydrocarbon group. Here, the long-chain hydrocarbon group may be a saturated hydrocarbon group having 6 or more, 10 or more, 15 or more, or 20 or more, preferably 10 or more or 23 or more carbon atoms. Here, the hydrocarbon group may be linear or branched, and is preferably an alkyl group. Specific examples of the hydrocarbon group are hexyl group (6 carbon atoms), octyl group (8 carbon atoms), lauryl group (12 carbon atoms), myristyl group (14 carbon atoms), stearyl group (18 carbon atoms), behenyl group (22 carbon atoms), tricosyl group (23 carbon atoms), lignoceryl group (tetracosyl group, 24 carbon atoms), cerotyl group (hexacosyl group, 26 carbon atoms), montyl group (octacosyl group, 28 carbon atoms), melissyl group (triacontane group, 30 carbon atoms), dotriacontane group (32 carbon atoms).

[0126] In terms of being easy to manufacture industrially and being easily available, R which is a long-chain hydrocarbon group 51 and R 53 Other than R 51 and R 53 are 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 being easy to manufacture industrially and being easily available, a may be 40 or less, 30 or less, 20 or less, and is preferably 30 or less.

[0128] The sum of a and b is 5 to 200. In terms of being easy to manufacture industrially, being easily available, and being easy to handle, 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 or 2 or 3, and the upper limit of b may be 150, 10, or 5.

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

[0130] R51 and R 53 group (for example, when represented by the following formula (S2), R 51 and R 52 group and R 53 group), it is preferable that 50 mol% or more of the total is a methyl group.

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

[0132] For example, the silicone has the formula: (R 53 )3Si - O - [-Si(R 51 )2 - O - ] a -[-Si(R 51 )(R 52 ) - O - ] b -Si(R 53 )3(S2) [In the formula, each of R 51 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, each of R 52 independently represents a long-chain hydrocarbon group, each of R 53 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.] It may be a polymer represented by. 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 they do not have these groups.

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

[0134] The silicone can be synthesized by a conventionally known method. The silicone can be obtained, for example, by hydrosilylating an α-olefin with a silicone having an SiH group.

[0135] Examples of the silicone having an SiH group include methylhydrogen silicone having a degree of polymerization of 10 to 200, or a copolymer of dimethylsiloxane and methylhydrogensiloxane. Among these, methylhydrogen silicone is preferred in terms of easy industrial production and easy availability. Hydrogen silicone (e.g., methylhydrogen silicone) means that a part of the side chain of polydiorganosiloxane is substituted with hydrogen, and the hydrogen atom is directly bonded to the silicon atom. When using hydrogen silicone, a catalyst may be used to improve the reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine-based catalysts can be used. As these catalysts, metal organic acid salts are preferred, and fatty acids are preferred as the organic acid. From the viewpoint of excellent handleability, zinc stearate or the like can be used. It is preferable to use the catalyst in an amount of 10 to 40% based on methylhydrogen silicone because the effect is easily exerted. Amino-modified, epoxy-modified silicone, carboxy-modified silicone, and methylhydrogen silicone may be mixed in two or more kinds. All of them are silicones having reactive groups and preferably have film-forming properties. The film-forming property means that after each of these silicones is attached to the fiber surface in an emulsion state, a solid film is formed instead of an oil-like or gel-like state.

[0136] α-olefin is a compound that serves as the source of long-chain hydrocarbon groups in silicone. Specific examples of α-olefin are 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triacontene, and 1-dotriacontene. The hydrosilylation reaction may be carried out by reacting the silicone having the above SiH group with α-olefin stepwise or at once in the presence of a catalyst as needed.

[0137] The amounts of the silicone having the SiH group and α-olefin used in the hydrosilylation reaction can be appropriately selected according to the SiH group equivalent of the silicone having the SiH group, the number average molecular weight, etc.

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

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

[0140] (Reactive silicone) The silicone may contain reactive silicone. Examples of the reactive silicone include polysiloxanes having reactive groups in side chains, one terminal, both terminals, or side chains and both terminals. From the viewpoint of excellent anti-slip properties and excellent water repellency at the same time, a polysiloxane having reactive groups in side chains and / or both terminals may be used. The reactive silicone is not particularly limited as long as it has a reactive group in the molecule. For example, amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, hydrogen-modified silicone, etc. may be mentioned. The reactive silicone may be one in which one or more substituents in the above formula (S1) or formula (S2) are replaced with reactive groups.

[0141] Examples of the amino-modified silicone 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 the organic group to which the amino group is bonded include the following. 2-aminoethyl group, N-methyl-2-aminoethyl group, N,N-dimethyl-2-aminoethyl group, N-ethyl-2-aminoethyl group, N,N-diethyl-2-aminoethyl group, N,N-methylethyl-2-aminoethyl group, 3-aminopropyl group, N-methyl-3-aminopropyl group, N,N-dimethyl-3-aminopropyl group, N-ethyl-3-aminopropyl group, N,N-diethyl-3-aminopropyl group, N,N-methylethyl-3-aminopropyl group. These functional groups may be in the side chain or at the terminal of the polysiloxane.

[0142] Examples of the epoxy-modified silicone 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. Usually, it is bonded in the form of a glycidyl ether to the above organic group. Examples of such a functional group include a 3-glycidoxypropyl group and a 2-glycidoxyethyl group. These functional groups may be located in the side chain or at the terminal of the polysiloxane.

[0143] Examples of the carboxy-modified silicone 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 2 or more carbon atoms. The divalent aromatic group preferably has 6 or more carbon atoms. Examples of such a functional group include a 3-carboxypropyl group and a 2-carboxyethyl group. These functional groups may be located in the side chain or at the terminal of the polysiloxane.

[0144] (Silicone resin) The silicone may contain a silicone resin. The silicone resin is a silicone resin composed of at least one selected from the units of R3SiO 1 / 2 (M unit), RSiO 3 / 2 (T unit) and SiO 4 / 2 (Q unit), where R is a linear or branched monovalent alkyl group having 1 to 18 carbon atoms (excluding the silicone resin composed only of M units and only of Q units). From the viewpoint of exerting the effects of the present application, it is preferable that the silicone resin (B) does not contain the R2SiO 2 / 2 (D unit).

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

[0146] When the silicone resin contains R2SiO 2 / 2 units (D units), the low slipperiness of the water repellent composition may be impaired. Further, a silicone resin composed only of Q units may inhibit the water repellent performance as a water repellent composition.

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

[0148] Further, the silicone resin (B) can contain a structural unit containing a hydroxyl group bonded to a silicon atom. Specifically, units such as (HO)RSiO 2 / 2 units, (HO)2RSiO 1 / 2 units, (HO)SiO 3 / 2 units, (HO)2SiO 2 / 2 units, (HO)3SiO 1 / 2 units are exemplified, and a part of the hydroxyl group may be an alkoxy group represented by an RO group.

[0149] The sol containing silicone resin can be obtained by a production method in which organodisiloxane, tetraalkoxysilane, and its partial hydrolysis condensate are uniformly dispersed and polymerized in water containing a surfactant, as described in Patent 3852921, or by a production method in which the following silane compound is hydrolyzed in water.

[0150] A manufacturing method for hydrolyzing a silane compound in water will be described in detail. As a raw material for manufacturing, any silane compound having a hydrolyzable group of chlorine or alkoxy, containing one, three, or four hydrolyzable groups, and having an alkyl group satisfying the above conditions can be used.Specifically, silane compounds that can be used include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrichlorosilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrichlorosilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, 2-ethylhexyltrichlorosilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, decyltriethoxysilane, cetyltrichlorosilane, cetyltrimethoxysilane, cetyltriethoxysilane, stearyltrichlorosilane, stearyltrimethoxysilane, stearyltriethoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, dimethylethylchlorosilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylpropylchlorosilane, dimethylpropylmethoxysilane, dimethylpropylethoxysilane, dimethylisopropylchlorosilane, dimethylisopropylmethoxysilane, dimethylisopropylethoxysilane, dimethylhexylchlorosilane, dimethylhexylmethoxysilane, dimethylhexylethoxysilane, dimethyldecylchlorosilane, dimethyldecylmethoxysilane, dimethyldecylethoxysilane, dimethylcetylchlorosilane, dimethylcetylmethoxysilane, dimethylcetylethoxysilane, dimethylstearylchlorosilane, dimethylstearylmethoxysilane, dimethylstearylethoxysilane, and partial hydrolyzates thereof. However, the silane compounds that can be used are not limited to these.From the viewpoints of operability, ease of removing by-products, and ease of obtaining raw materials, it is more preferable to use methoxysilane or ethoxysilane. One or a mixture of two or more of these silane compounds may be used.

[0151] As a method for hydrolyzing a silane compound in water, a generally known common method can be used. That is, a method in which a hydrolysis reaction is carried out while dropping a silane compound into water, or a method in which water and a silane compound are mixed all at once and then a hydrolysis reaction is carried out. When carrying out the hydrolysis reaction, a hydrolysis catalyst may be used. As the hydrolysis catalyst, a conventionally known catalyst can be used, and it is preferable to use an acidic or alkaline one. In the case of an acidic catalyst, hydrogen halide, carboxylic acid, sulfonic acid, acidic or weakly acidic inorganic salts, solid acids such as ion exchange resins are preferable. In the case of an alkaline catalyst, alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, alkali metal silanolates such as sodium silanolate and potassium silanolate, amines such as triethylamine, diethylamine, aniline, and aqueous ammonia can be used. It is preferable to adjust the addition amount so that the pH of the aqueous solution becomes 2 to 7 and 7 to 12. Further, after the reaction is completed, a neutralizing agent for neutralizing the acidic or alkaline catalyst may be added as necessary.

[0152] A surfactant may be added to the aqueous solution to disperse the silane compound and the hydrolysis reaction product in water. There are no particular restrictions on the surfactant. For example, anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, and alkyl phosphates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene oxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and polyoxyethylene fatty acid esters; cationic surfactants such as quaternary ammonium salts and alkylamine acetates; amphoteric surfactants such as alkyl betaines and alkyl imidazolines can be used, and these can be used alone or in combination of two or more. Also, those showing acidity or alkalinity as surfactants can also be used as hydrolysis catalysts. There are no particular restrictions on the addition amount when adding the surfactant, but it is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the silane compound. If it is less than 1 part by weight, the effect of adding the surfactant cannot be sufficiently obtained, and if it is more than 50 parts by weight, the water repellency of the water repellent may be impaired.

[0153] To the mixture of water and the silane compound, a hydrolysis catalyst and a surfactant may be added as necessary, and a hydrolysis reaction may be carried out at 0 to 90 °C for 10 minutes to 24 hours. Then, a silicone resin can be obtained by carrying out a neutralization reaction as necessary. Also, by-products such as alcohols and neutral salts produced by the hydrolysis reaction can be removed by distillation under reduced pressure or filtration. Various additives can be blended into this silicone resin. For example, a preservative, a thickener, etc. can be blended according to 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 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, or 20 part by weight or more with respect to 100 parts by weight of the non-fluorine copolymer (A). The amount of silicone may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less with respect to 100 parts by weight of the non-fluorine copolymer (A).

[0155] 〔Wax〕 In addition to the hydrophobic monomer (a1), the water repellent composition in the present disclosure preferably contains wax. By containing wax, it can have good water repellency and anti-slip properties. The water repellent composition in the present disclosure may contain both silicone and wax, or may contain only one of silicone and wax.

[0156] Examples of wax include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (such as polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, animal and plant wax, and mineral wax. Paraffin wax is preferred. Specific examples of the compounds constituting the wax are normal alkanes (for example, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane), normal alkenes (for example, 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane). The carbon number of the compounds constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500, 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 with respect to 100 parts by weight of the non-fluorine copolymer (A). The amount of wax may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less with respect to 100 parts by weight of the non-fluorine copolymer (A).

[0159] 〔Inorganic Particles〕 The water repellent composition in the present disclosure may contain inorganic particles. By containing inorganic particles, water repellency and slip resistance can be more favorably imparted. The inorganic particles may be an aluminum compound (for example, alumina), a silicon compound (for example, silica), a titanium compound, or the like. These may be used alone or in combination of two or more. The inorganic particles may be subjected to hydrophilic surface treatment or 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. By being in the above range, it can have both good water repellency and slip resistance. The average primary particle diameter can be measured with a microscope (scanning electron microscope or transmission electron microscope). Specifically, an arbitrary position of the fabric is observed from above at an arbitrary magnification with a microscope. Next, when the particle shape is spherical, its diameter, and when it is non-spherical, the average value of the longest diameter and the shortest diameter are regarded as the particle diameter (particle size). Measure the particle sizes of all the particles present in the field of view, move the field of view, and repeat measuring the particle sizes again to measure the particle sizes at 10 points or more, and take the average value as the average primary particle diameter.

[0161] (Amount of Inorganic Particles) The amount of the 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 with respect to 100 parts by weight of the non-fluorine copolymer (A). The amount of the inorganic particles may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less with respect 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. Preferably, it is a mixture of water and an organic solvent. By containing an organic solvent, it can have good water repellency and anti-slip properties at the same time.

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

[0164] (Amount of the 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 with respect 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 with respect 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 agent 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 agent composition.

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

[0167] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more based on 100 parts by weight of the non-fluorine 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 based on 100 parts by weight of the non-fluorine copolymer (A).

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

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

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

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

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

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

[0174] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols having 1 to 6 (especially 2 to 5) valences and 1 to 50 carbon atoms (especially 10 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0175] Examples of ester ethers are compounds in which an alkylene oxide (especially ethylene oxide) is added to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols having 1 to 6 (especially 2 to 5) valences and 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0176] Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamine. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 1 to 3 amino groups and 1 to 5 hydroxyl groups and 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0177] The polyhydric alcohol may be an alcohol having 2 to 5 valences and 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (for example having 5 to 50 carbon atoms).

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

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

[0180] The nonionic surfactant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [wherein, R 1 is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms or an acyl group, each of R 2 is independently the same or different and is an alkylene group having 3 or more carbon atoms (for example, 3 to 10), R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, q is 0 or a number of 1 or more.] and may be a compound represented by.

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

[0182] Specific examples of the nonionic surfactant include condensation products of ethylene oxide with hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 -C 18 ) amine, etc.

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

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

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

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

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

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

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

[0190] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, betaine acetates, etc. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, fatty acid amide propyldimethylaminoacetic acid betaine, etc. can be mentioned.

[0191] The surfactant may be one or a combination of two or more of nonionic surfactants, cationic surfactants, and amphoteric surfactants.

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

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

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

[0195] The hardener may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, 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, 1,03-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as 2,6-diisocyanatomethyl caproate, and lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane and other aliphatic triisocyanates. 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 the alicyclic polyisocyanate are 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

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

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

[0200] Derivatives of the polyisocyanates include, for example, various derivatives such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretoimines, isocyanurates, iminooxadiazinediones of the above-described polyisocyanate compounds. These may be used alone or in combination of two or more thereof.

[0201] These polyisocyanates can be used singly 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 obtained by blocking the isocyanate groups of the polyisocyanate compound with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable even in an aqueous solution and can be used in the same aqueous solution as the water repellent composition.

[0202] The blocking agent blocks free isocyanate groups. The blocked polyisocyanate compound can, for example, regenerate isocyanate groups by heating to 100 °C or higher, for example, 130 °C or higher, and can easily react with hydroxyl groups. Examples of the blocking agent are phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, etc. The polyisocyanate compounds can be used alone or in combination of two or more.

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

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

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

[0206] The silicone, wax, inorganic particles, liquid medium, dispersant, surfactant, or curing agent mentioned above may be added after producing the non-fluorine copolymer (A), or the monomer of the non-fluorine copolymer (A) may be polymerized in the presence of the silicone, wax, inorganic particles, liquid medium, dispersant, surfactant, or curing agent mentioned above to produce the non-fluorine copolymer (A). below, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less.

[0207] 〔Other components〕 The water-repellent composition may contain other components in addition to the above components. After producing the non-fluorine copolymer (A), other components may be added. Examples of other components include water-repellent and / or oil-repellent agents, slip inhibitors, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above components, as other components, there are hand modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying rate adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage preventers, washing wrinkle preventers, shape retainers, drape retainers, ironing property improvers, brightening agents, whitening agents, fabric softening clay, migration inhibitors such as polyvinylpyrrolidone, polymer dispersants, soil release agents, scum dispersants, fluorescent brightening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, defoaming agents, silk protein powder, surface-modified products thereof, and emulsion dispersions that can impart silk-like texture and functions such as water absorption and release, specifically K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (Jomo), Silkgen G Soluble S (Ichimaru Pharcos), nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units, for example, contamination preventives such as FR627 manufactured by Gohsen Chemical Industry Co., Ltd., SRC-1 manufactured by Clariant Japan, etc. 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, primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate esters, phosphonates, and phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and its derivatives; nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives, etc. These may also be ionic conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic, and zwitterionic ionic conductive groups. These may be used alone or in combination of two or more.

[0209] (Antibacterial and antifungal agent) An antibacterial and antifungal agent is at least one antibacterial and antifungal agent that suppresses 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 for Antibacterial and Antifungal Agents 1998 VOL.26 can be used.

[0210] Amine-based such as Bis(3-aminopropyl)dodecylamine (trialkyltriamine), Alcohol-based 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 (propronol, pronozol, pronocott), etc. Aldehyde-based such as 1,5-Pentanediol (glutaraldehyde), Formaldehyde (formaldehyde), α-Bromocinnamic aldehyde (α-bromocinnamaldehyde), etc. Isothiazoline-based compounds such as 2-n-Octyl-4-isothiazolin-3-one (Scan M-8), 5-Chloro-2-methyl-4-isothiazolin-3-one / 2-Methyl-4-isothiazolin-3-one (Kathon CG, NS-500W), 1,2-Benzisothiazolone-3 (BIT), 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), Methyl-2-benzimidazole carbamate (2-Benzimidazolylcarbamic acid methyl, Preventol BCM), Ester-based compounds such as Glycerol laurate (Lauricidin, Glycerol monolaurate, Monoglyceride), Oxazolidine-based compounds such as 4,4-Dimethyl-1,3-oxazolidine (Biopane CS-1135, Oxazine A), Carbanilide-based compounds such as 3,4,4'-Trichlorocarbanilide (Triclocarban, Trichlorocarbanilide), 4,4'-Dichloro-3-(3-Fluoromethyl)-carbanilide (Halocarban, Chlorflucarban), Carbamate-based compounds such as 3-Iodo-2-propynylbutyl carbamate (Glycidal), Carboxylic acids such as Benzoic acid, Flexa-2,4-dienoic acid, 2-propanylacrylic acid, Octanoic acid, Propionic acid, Undecylenic acid, Potassium hexa-2,4-dienoic acid, Potassium propionate, Calcium propionate, Sodium benzoate, Sodium propionate, Magnesate(2-),bis(2-carboxybenzene carboperoxato)dihydrogene, Zinc undecylenate, etc. Quinoline-based compounds such as 8-hydroxyquinoline, Bis(quinolin-8-olate)copper (quinoline copper, oxine copper, 8-quinolinol copper), Sulfide-based compounds such as Bis(dimethylthiocarbamoyl)disulfide (TMTD, thiuram), Diphenyl ethers such as 2,4,4'-Trichloro-2'-hydroxydiphenyl (Triclosan, Irgasan DP300), Sulfamides such as N,N-Dimethyl-N'-(fluorodichloromethylthio)-N"-phenylsulfamide (Cyclofluanid, Preventol A4-S) and N-Dichlorofluoromethylthio-N',N'-dimethyl-Np-torylsulfamide (Trifluanid, Preventol A5) Proteins such as Protamine (milt protein, milt hydrolysate, nuclear protein) and Hen egg lysozyme (egg white lysozyme) Thiazole-based such as 2-(4-Thiocyanomethylthio)benzothiazol (benzothiazole), Thiocarbamate-based such as Sodium N-methyldithiocarbamate (sodium N-methyldithiocarbamate, carbam sodium), Hexahydro-1,3,5-tris(hydroxyethyl)-S-triadine (Biopan GK, triazine), Triazine-based such as CAVINON(100,200) (Cavinon(100,200)), α-[2-(4-Chlorophenyl)ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol (Debutaconazole), Tropolone-based such as 4-Isopropyl-2-hydroxy-cyclohepta-2,4,6-triene-1-one (hinokitiol, β-tsuyapurin), Nitrile-based such as 2,4,5,6-Tetrachloroisophthalonitrile (tetrachloroisophthalonitrile), 1,2-Dibromo-2,4-dicyanobutane (Tectamar 38), Biguanide-based such as 1,1'-(Hexamethylene bis[5-(4-chlorophenyl)biguanide]digluconate (chlorhexidine gluconate), Bis(p-chlorophenyldiguanide)hexane dihydrochloride (chlorhexidine hydrochloride), Hydantoin-based such as 1-Bromo-3-chloro-5,5'-dimethyl hydantoin (Dantobrom), 1,3-Bis-(hydroxymethyl)-5,5'-dimethyl hydantoin (Glydant, Dantogard), Pyridine-based compounds such as Sodium pyridine thiol-1-oxide (sodium pyrithione), Zinc bis(2-pyridylthio-1-oxide) (zinc pyrithione, zinc omadine, ZPT), 2,3,5,6-Tetrachloro-4-(methylsulphonyl)pyridine (densyl), Copper bis(2-pyridylthio-1-oxide) (copper pyrithione, copper omadine, CuPT), Phenol-based compounds such as 2-Isopropyl-5-methylphenol (thymol, 2-isopropyl-5-methylphenol), 3-Methyl-4-iso-propylphenol (isopropylmethylphenol, pirozole), o-Phenylphenol (OPP, orthophenylphenol), Phenol (phenol, carbolic acid), Butyl-p-hydroxybenzoate (butyl paraben), Ethyl-p-hydroxybenzoate (ethyl paraben), Methyl-p-hydroxybenzoate (methyl paraben), Propyl-p-hydroxybenzoate (propyl paraben), m-Methylphenol (m-cresol), o-Methylphenol (o-cresol), p-Methylphenol (p-cresol), o-Phenylsodiumphenoxide (sodium orthophenylphenol), 2-Benzyl-4-chlorophenol (chlorophen), p-Chlorophenol (parachlorophenol), 4-Chloro-3,5-dimethylphenol (parachlorometaxylenol), 2-Methyl-3-chlorophenol (parachloromethacresol), Phthalimide-based compounds such as N-(Fluorodichloromethylthio)-phthalimide (fluoropholpet, briventol A3), Peptide-based compounds such as ε-Poly-L-lysine (polylysine, ε-polylysine), Morpholine-based such as 4-(2-Nitrobutyl)morpholine / 4,4'-(2-nitrotrimethylene)dimorpholine (Bio-Pan P-1487), Iodine-based such as Diiodomethyl-p-trylsulfone (Diiodomethyl para-tolyl sulfone), Polyvinylpyrolidone iodide (Polyvinylpyrrolidone iodine, Povidone iodine, Isodine), p-Chlorophenyl-3-iodopropagyl formal (Para-chlorophenyl-3-iodopropagyl formal), 3-Bromo-2,3-diiodo-2-propenylethylcarbonate (Sample Plus), Chlorine-based such as Sodium hypochlorite (Sodium hypochlorite, Sodium chlorite), Sodium dichlorinated isocyanurate (Sodium dichloroisocyanurate), Trichlorinated isocyanuric acid (Trichloroisocyanuric acid), Peroxide-based such as Hydrogen peroxide (Hydrogen peroxide), Chlorine dioxide (Stabilized chlorine dioxide, Biotok), Peracetic acid (Peracetic acid), Metal salt-based such as Copper naphthenate (Copper naphthenate), Silver / Zirconium phosphate (Novaron AG300), Silver chloride / Titanium oxide (Silver chloride / Titanium oxide), Silver-Zinc / Calcium phosphate (Silver / zinc calcium phosphate, Silver Ace), Silver-Zinc / Zeolite (Silver zinc aluminosilicate, Silver zinc zeolite), Zinc oxide, Silver / Zirconium phosphate (Novaron AGZ330), N-Stearoyl-L-glutamic acid AgCu salt (Holon Killer), Antibiotic systems such as 1-L-(1,3,5 / 2,4)-1,5-diamino-4-O-(2,5-dideoxy-α-D-glucopyranosyl)-2,3-cyclohexandiol (ST-7), Oxide systems such as ethylene oxide (EO), propylene oxide (PO), Quaternary ammonium salt systems such as 4,4'-(tetramethylenedicarbonyldiamino)bis(1-decylpyridinium bromide) (dimer 135), decyldimethylbenzylammonium chloride (benzalkonium chloride), didecyldimethylammonium chloride (bardac 2250 / 80), diisobutylphenoxyethoxydimethylbenzylammonium chloride (benzethonium 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 chloride (bardac 170P), 5-(trimethoxysilyl)propyldimethyloctadecylammonium (DC-5700), hexadecyl pyridinium chloride, Carbohydrates such as β-1,4-poly-D-glucosamine (chitosan), Examples include urea-based compounds such as N'-(3,4-dichlorophenyl)-N,N-dimethylurea (Duron, DCMU, Briventol A6). In particular, isothiazolin-based antibacterial and antifungal agents such as 2-n-octyl-4-isothiazolin-3-one (Scan M6), a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one (BIT), and N-n-butyl-1,2-benzisothiazolin-3-one (BBIT) are preferred.

[0211] In particular, 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), and N-n-butyl-1,2-benzisothiazolin-3-one (BBIT) are preferred. These antibacterial and antifungal agents can be used alone or in combination of two or more.

[0212] The amount of the antibacterial and antifungal agent may be 1.5 ppm or more, 7.5 ppm or more, 30 ppm or more, 75 ppm or more, or 100 ppm or more as the active ingredient concentration based on the total amount of the water repellent composition, and may also be 600 ppm or less, 450 ppm or less, 300 ppm or less, 200 ppm or less, 150 ppm or less, or 100 ppm or less. For example, the amount of the antibacterial and antifungal agent may be 1.5 - 450 ppm, preferably 7.5 - 300 ppm, particularly preferably 75 - 150 ppm based on the total amount of the 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 also be 1500 ppm or less, 1000 ppm or less, 750 ppm or less, 450 ppm or less, 300 ppm or less, 200 ppm or less, 150 ppm or less, or 150 ppm or less, based on the non-fluorine copolymer (A). For example, the amount of the antibacterial and antifungal agent may be 4.5 to 1350 ppm, preferably 22.5 to 900 ppm, particularly preferably 225 to 450 ppm, based on the non-fluorine copolymer (A).

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

[0215] (Preservative) The preservative can be mainly used to enhance the antiseptic power and bactericidal power and maintain the preservability during long-term storage. Examples of the preservative include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, and the like. The amount of the preservative is preferably 0.0001 to 1% by weight based on the total weight of the water-repellent composition. When the amount of the preservative is not less than the lower limit value of the above range, the addition effect of the preservative can be sufficiently obtained, and when it is not more than the upper limit value, the storage stability of the water-repellent composition is good.

[0216] (Antibacterial agent) The antibacterial agent is a component having the effect of suppressing the growth of bacteria on the fiber and further suppressing the generation of unpleasant odors derived from decomposition products of microorganisms. Examples of the antibacterial agent include cationic bactericides such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanide hydrochloride, 8-hydroxyquinoline, polylysine, and the like.

[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. and emits them. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, 4-t-butyl-4'-methoxybenzoylmethane, and the like.

[0218] (Deodorant) Examples of deodorants include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, aminocarboxylic acid-based metal complexes (zinc complex of methylglycine diacetic acid trisodium described in International Publication No. 2012 / 090580), and the like.

[0219] (Fragrance) The fragrance is not particularly limited, but the list of fragrance raw materials that can be used can be found in various documents, such as "Perfume and Flavor Chemicals", Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994) and "Synthetic Fragrances, Chemistry and Product Knowledge", written by Motokazu Indoh, Chemical Industry Daily Co., Ltd. (1996) and "Perfume and Flavor Materials of Natural Origin", Steffen Arctander, Allured Pub. Co. (1994) and "Encyclopedia of Scents", edited by the Japan Flavor Association, Asakura Shoten (1989) and "Perfumery Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower oils and Floral Compounds In Perfumery", Danute Lajaujis Anonis, Allured Pub. Co. (1993), etc., and each is incorporated by reference as part of the disclosure of this specification.

[0220] (Amount of other components) The amount of the other component 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 with respect to 100 parts by weight of the non-fluorine copolymer (A). The amount of the other component 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 with respect to 100 parts by weight of the non-fluorine copolymer (A).

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

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

[0223] Examples of the polymerization method include suspension polymerization and emulsion polymerization, and emulsion polymerization can be mentioned from the viewpoint of obtaining an emulsion of the non-fluorine copolymer (A).

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

[0225] The blending ratio of the surfactant may be, for example, 1 part by weight or more, preferably 3 parts by weight or more, and, for example, 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the total amount of the monomers (specifically, a hydrophobic monomer (a1) having a hydrocarbon group with 2 to 40 carbon atoms, at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride, an optionally blended cyclic hydrocarbon group-containing monomer (a3), an optionally blended crosslinkable monomer (a4), and an optionally blended other monomer (a5); 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, based on 100 parts by weight of the total amount of the monomers. As the liquid medium, those mentioned above may be used. For example, the liquid medium may be water. In emulsion polymerization, an organic solvent may be further added. As the organic solvent, those of the liquid media mentioned above may be used. The organic solvent may be a water-soluble glycol-based solvent, for example, ethylene glycol or propylene glycol.

[0227] In emulsion polymerization, the above-mentioned organic acid 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 part by weight or more, 0.1 part by weight or more, and 1 part by weight or less, 0.5 part by weight or less, based on 100 parts by weight of the total amount of the monomers.

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

[0229] Examples of the emulsifier include known emulsifiers, such as cationic emulsifiers and anionic emulsifiers.

[0230] In addition, the above surfactant can also be used as the emulsifier.

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

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

[0233] The reactive emulsifier is an emulsifying dispersant having radical reactivity, that is, an emulsifier having one or more polymerizable unsaturated groups in the molecule, and is an emulsifier copolymerizable with the above-mentioned monomers. Examples of the reactive emulsifier include the reactive emulsifier described in JP-A-2017-25440, and preferably, the reactive emulsifier represented by the following formula.

Chemical 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, and preferably represents an oxyethylene group

[0236] If the reactive emulsifier is the reactive emulsifier represented by the above formula, the product stability of the aqueous dispersion (water repellent composition) is improved without reducing the water repellency. As the reactive emulsifier represented by the above formula, preferably, polyoxyethylene alkylphenol and the like can be mentioned.

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

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

[0239] Also, the compounding ratio of the emulsifier may be, for example, 8 parts by weight or more and, for example, 20 parts by weight or less with respect to 100 parts by weight of the total amount of the isocyanate derivative (B) and the non-fluorine copolymer (A).

[0240] Also, the compounding ratio of the emulsifier may be, for example, 0.5% by weight or more and, for example, 5% by weight or less with respect to the water-repellent composition.

[0241] And after mixing the above-described components, the mixed solution is stirred, ultrasonic waves are applied to the mixed solution, and the mixed solution is emulsified.

[0242] As a method of stirring, for example, a disperser such as a homomixer (homomixer), an ultrasonic homogenizer, a pressure-type homogenizer, a molder, a porous membrane press-in disperser, etc. is used, and preferably, a homomixer is used.

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

[0244] Next, when a part of the monomers is blended when preparing the above mixed solution, the remaining part of the above monomers is blended into this mixed solution.

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

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

[0247] The blending ratio of the polymerization initiator may be, for example, 0.01 part by weight or more and, for example, 10 parts by weight or less based on 100 parts by weight of the monomer.

[0248] In addition, a chain transfer agent can be added to this mixed solution if necessary.

[0249] Examples of the chain transfer agent include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly, (for example, alkyl mercaptan having 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. Preferably, lauryl mercaptan is used.

[0250] The blending ratio of the chain transfer agent may be, for example, 0.01 part by weight or more and, for example, 10 parts by weight or less based on 100 parts by weight of the monomer.

[0251] Then, this mixed solution is heated to polymerize the monomer.

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

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

[0254] The third method is the same as the above production method except that the monomers constituting the above non-fluorine copolymer (A) are polymerized in the absence of the isocyanate derivative (B). The non-fluorine 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] Further, after polymerizing the monomers to prepare the non-fluorine copolymer (A), the obtained non-fluorine copolymer (A) and the isocyanate derivative (B) can also be blended (fourth method). Further, first, after polymerizing the monomers to prepare the non-fluorine copolymer (A), the obtained non-fluorine copolymer (A), the isocyanate derivative (B), a surfactant, and a liquid medium can also be blended (fifth method).

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

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

[0258] As the polymerization initiator, the above polymerization initiator may be used. The blending ratio of the polymerization initiator may be, for example, 0.01 part by weight or more, and, for example, 20 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the monomers.

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

[0260] The blending 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 with respect to 100 parts by weight of the monomer.

[0261] As 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 longer and, for example, 10 hours or shorter.

[0262] Thus, the non-fluorine copolymer (A) is obtained.

[0263] And after producing the non-fluorine copolymer (A) by solution polymerization, the organic solvent is removed, and an emulsion of the non-fluorine copolymer (A) can be prepared by blending the non-fluorine copolymer (A) together with an isocyanate derivative (B) in a surfactant and a liquid medium.

[0264] <Uses of the water repellent composition> Examples of the uses of the water repellent composition in the present disclosure include external treatment agents (surface treatment agents) or internal treatment agents, water repellents (water repellents, oil repellents, water and oil repellents, etc., particularly water repellents), antifouling agents, soil release agents, release agents, mold release agents (external mold release agents or internal mold release agents), and the like.

[0265] <Method for manufacturing a treated product> The method for manufacturing 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 product] Examples of the substrate treated with the water repellent composition of the present disclosure include textile products, stone, filters (e.g., electrostatic filters), dust masks, parts of fuel cells (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster, etc. Various examples can be given as textile products. For example, animal and plant natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers, or mixed fibers thereof can be mentioned. As an example of the substrate treated with the water repellent composition, an example of a woven or knitted fabric will be described in detail.

[0267] (Woven or knitted fabric) ·Manufacturing method of woven or knitted fabric The woven or knitted fabric can be obtained by weaving or knitting the above-mentioned mixed and entangled yarns to obtain a gray fabric, and then subjecting this to post-processing and water repellent processing. Weaving or knitting can be performed using known weaving machines and knitting machines, and the preparatory processes prior to weaving or knitting can also use known equipment.

[0268] Also, in the post-processing, first, the gray fabric is scoured and relaxed. The scouring and relaxation can be performed by a continuous method or a batch method at a temperature of 80 to 130°C. Usually, it is preferably performed by a batch method at 100°C or lower, and particularly preferably performed using a high-pressure liquid flow dyeing machine equipped with a jet nozzle.

[0269] After refining and relaxing, preset the knitted or woven fabric. The preset is usually carried out by dry heat treatment at 170 - 200 °C for 30 - 120 seconds using a pin tenter. After presetting, dye it based on the conventional method, and then perform a final set as necessary.

[0270] After post - processing, the knitted or woven fabric may be subjected to water - repellent treatment. In the water - repellent treatment, first, prepare an aqueous solution containing a water - repellent agent (which may be the water - repellent agent composition in the present disclosure). Next, based on methods such as padding method, spraying method, kiss roll coater method, slit coater method, etc., apply the above aqueous solution to the knitted or woven fabric after the above post - processing, and perform dry heat treatment at 105 - 190 °C for 30 - 150 seconds. The above aqueous solution may also contain a cross - linking agent, a softening agent, an antistatic agent, etc. as necessary. After the water - repellent treatment, the knitted or woven fabric may be calendered for further improvement of water - repellent performance.

[0271] The knitted or woven fabric is preferably used for clothing applications, especially for uniform wear, ladies' wear, and sportswear applications.

[0272] · Laminated fabric It may be provided as a laminated fabric with a moisture - permeable and waterproof layer provided on one side of the knitted or woven fabric of the present disclosure. The moisture - permeable and waterproof layer may be directly laminated to the knitted or woven fabric, or may be laminated to the knitted or woven fabric via an adhesive layer. When using the laminated fabric of the present disclosure for clothing applications, etc., it is arranged such that the knitted or woven fabric side is exposed to rainwater, etc.

[0273] · Moisture - permeable and waterproof layer The moisture - permeable and waterproof layer is a layer covering one surface of the knitted or woven fabric, and is a layer formed by a resin having waterproofness and moisture permeability.

[0274] The moisture-permeable waterproof layer may be formed by directly applying a resin (the resin constituting the moisture-permeable waterproof layer) to the woven or knitted fabric, or may be laminated on one side of the woven or knitted fabric via the adhesive layer described later. In the present disclosure, a conjugated fiber interlaced yarn having fine protrusions caused by loops or slack in the woven or knitted fabric is used. Therefore, due to the strong entanglement of the protrusions with the adhesive layer or the moisture-permeable waterproof layer, an anchor effect is exhibited, making it even more difficult for the woven or knitted fabric and the moisture-permeable waterproof layer to peel off. When using an ordinary woven or knitted fabric (a woven or knitted fabric in which the above-mentioned protrusions are not sufficiently maintained on the surface), the anchor effect may not be fully exhibited, and in such cases, the woven or knitted fabric and the moisture-permeable waterproof layer tend to be easily peeled off.

[0275] The resin constituting the moisture-permeable waterproof layer is not particularly limited, but is preferably composed of a polyurethane resin as the main component. For example, it is preferably contained in a proportion of 80% by weight or more of the polyurethane resin. Polyurethane resin is generally suitable for forming a resin layer having moisture permeability and waterproofness. Among them, considering moisture permeability, a microporous type is preferable, but when it is likely to be exposed to long-term rainfall or repeated use such as washing is assumed, non-porous moisture-permeable urethane of a non-microporous type may be used.

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

[0277] The moisture-permeable waterproof layer may have a microporous structure or a non-porous structure. Further, when having a microporous structure, in order to ensure desired moisture permeability, inorganic fine powder can be contained in the moisture-permeable waterproof layer.

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

[0279] The thickness of the moisture-permeable waterproof layer is preferably 5 μm or more, more preferably 10 to 30 μm. When the thickness is within the above range, the balance between waterproofness and moisture permeability is excellent, and there are advantages in terms of texture and tear strength.

[0280] · Adhesive layer The laminated fabric preferably includes an adhesive layer. That is, it is preferable that the woven or knitted fabric and the moisture-permeable waterproof layer are laminated via an adhesive layer. The reason for this is described below. In the present disclosure, as the woven or knitted fabric, as described above, a fabric having fine protrusions caused by loops or slack on the surface is adopted. Therefore, due to the strong entanglement of the protrusions with the adhesive layer, an anchor effect is exhibited, making it even more difficult for the woven or knitted fabric and the moisture-permeable waterproof layer to peel off.

[0281] Also, when directly laminating a moisture-permeable waterproof layer on the above-mentioned woven or knitted fabric by, for example, a coating method, the protrusions on the surface of the woven or knitted fabric may pierce through the moisture-permeable waterproof layer, resulting in the formation of pinholes and inferior water resistance and strength. There is also a concern that the coating may not be uniform, causing thickness unevenness in the moisture-permeable waterproof layer. To prevent this, if the surface of the woven or knitted fabric is smoothed by, for example, calendering, the water repellency may decrease due to the reduction of protrusions or the air retention layer. Therefore, in the present disclosure, it can be said that it is preferable that the woven or knitted fabric and the moisture-permeable waterproof layer are laminated via an adhesive layer.

[0282] The type of adhesive constituting the adhesive layer is not particularly limited, but it is preferably one having excellent compatibility with the moisture-permeable waterproof layer. For example, when selecting a resin containing polyurethane resin as the main component as the resin constituting the moisture-permeable waterproof layer, it is preferable to adopt an adhesive layer made of a polyurethane-based adhesive. The polyurethane-based adhesive may be of any structure such as ether-based, ester-based, or polycarbonate-based, but from the viewpoint of imparting excellent moisture permeability, an ether-based one is preferably mentioned.

[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 viewpoints of moisture permeability or texture. The pattern form is not particularly limited, and examples thereof include dot-like, linear, lattice-like, checkered pattern, and tortoise shell pattern, and it is preferable that any of them is uniformly arranged throughout.

[0284] As for the thickness of the adhesive layer, about 10 to 100 μm is preferable, and 20 to 80 μm is more preferable. If the thickness is less than 10 μm, it is difficult to obtain a durable laminated fabric even if the occupied area of the adhesive is increased. If it exceeds 100 μm, the manufacturing cost increases and there is a tendency that no further adhesiveness can be expected, and 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 (the side opposite to the side on which the woven or knitted fabric of the present disclosure is laminated in the moisture permeable waterproof layer). The lining fiber fabric can protect the moisture permeable waterproof layer and can be made to be more excellent in waterproof property (water pressure resistance) and strength. Further, by laminating the lining fiber fabric, the elongation of the entire laminated fabric can be suppressed. Therefore, it is possible to suppress the reduction of the protruding portion as a result of the protruding portion of the mixed fiber composite yarn being pulled by the elongation of the woven or knitted fabric due to the finishing process after lamination or the tension during wearing, and the water repellency can be maintained higher. Further, when the lining fiber fabric is laminated, the water repellency can be further improved.

[0286] Examples of the lining fiber fabric include various woven fabrics, knitted fabrics, etc. Among them, knitted fabrics are more suitable because the constituent yarns are more likely to protrude on the surface compared to woven fabrics and do not have a flat surface state, and the anchor effect is more exerted and it is difficult to peel from the moisture permeable waterproof layer. In particular, tricot knitted fabric is preferable because its stretchability is suppressed compared to knitted fabrics having other textures, so the knitting gaps do not become too large and the water repellency can be more effectively exhibited. Further, tricot knitted fabric is preferable also in that it can obtain a long live yarn during knitting and has few joints and can be laminated uniformly on the moisture permeable waterproof layer.

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

[0288] ·Properties of the laminated fabric The laminated fabric has excellent waterproofness. Suitable examples of the waterproofness of the laminated fabric of the present disclosure include, for example, the water level measured according to the water resistance test defined in JIS L 1092:2009 A method (low water pressure method) being, for example, 10000 mm or more, preferably 15000 mm or more, more preferably 16000 mm or more, and particularly preferably 20000 mm or more. The upper limit value of the water level is not particularly limited, and examples include, for example, 50000 mm or 25000 mm.

[0289] The laminated fabric has excellent moisture permeability. Suitable examples of the moisture permeability of the laminated fabric of the present disclosure include, for example, the moisture permeability measured according to JIS L 1099:2012 B-1 method (potassium acetate method) being, for example, 10000 g / m 2 ·for 24 h or more, preferably 15000 g / m 2 ·for 24 h or more, more preferably 20000 g / m 2 ·for 24 h or more. The upper limit value of the moisture permeability is not particularly limited, and examples include, for example, 40000 g / m 2 ·for 24 h or 35000 g / m 2 ·for 24 h·mm.

[0290] In the laminated fabric, delamination between the woven or knitted fabric and the moisture permeable and waterproof layer is suppressed. In the laminated fabric of the present disclosure, as a preferable example of the peel strength between the woven or knitted fabric and the moisture permeable and waterproof layer, the peel strength measured according to the method of JIS L 1089 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. In order to make the peel strength within the above range, for example, a woven or knitted fabric without calendering may be adopted, or an adhesive layer may be provided.

[0291] · Method for manufacturing laminated fabric The method for manufacturing the laminated fabric is not particularly limited, and for example, the first manufacturing method and the second manufacturing method shown below can be mentioned. First manufacturing method: It includes a step of forming the moisture permeable and waterproof layer by applying a resin constituting the moisture permeable and waterproof layer on the surface of the woven or knitted fabric. Second manufacturing method: It includes a step of forming an adhesive layer on the woven or knitted fabric or the moisture permeable and waterproof layer, and a step of bonding the woven or knitted fabric and the moisture permeable and waterproof layer through the adhesive layer.

[0292] It is preferable to maintain the protrusions on the surface of the woven or knitted fabric (that is, the woven or knitted fabric of the present disclosure described above) used for the laminated fabric as much as possible. For example, when the woven or knitted fabric is calendered to facilitate coating or the like, the fine protrusions of the conjugated and interlaced yarns are crushed and the surface becomes flat, and it may not be possible to achieve a specific water droplet rolling angle. Furthermore, when calendering is performed, the above-mentioned air retention layer cannot be sufficiently maintained, and the desired water repellency may not be achieved. Therefore, it is preferable to fully consider the conditions of calendering. For example, when calendering the woven or knitted fabric, normal conditions (for example, a temperature of 130°C or higher and a line pressure of 200 to 20,000 N / cm) that do not reduce the protrusions of the conjugated and interlaced yarns too much may be adopted. Note that calendering may be performed without heating.

[0293] In the first manufacturing method, as a method of applying a resin that forms a moisture-permeable waterproof layer on the surface of a knitted or woven fabric, for example, a coating method can be mentioned. In the coating method, a knife coater or a comma coater can be used. Also, 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, as a method of forming an adhesive layer on a knitted or woven fabric or a moisture-permeable waterproof layer, for example, a lamination method can be mentioned. In the lamination method, a method using a resin solution or a method using hot melt can be adopted for forming the adhesive layer. First, a clearance is provided on the surface of a release material (release paper, release cloth, release film, etc.) for a resin composition for forming a moisture-permeable waterproof layer (for example, a resin composition containing a resin and an organic solvent), and the moisture-permeable waterproof layer is formed while adjusting the thickness and heat-treated to be completely reacted to obtain a film. The release material can be appropriately removed after bonding or aging.

[0295] And then, an adhesive layer is formed on the knitted or woven fabric or the moisture-permeable waterproof layer. For example, in the case of a method using a resin solution, a two-component curing type polyurethane resin solution having a viscosity adjusted in the range of 500 to 5000 mPa·s may be applied entirely or in a pattern. Then, it is dried to form an adhesive layer, and the knitted or woven fabric and the moisture-permeable waterproof layer are bonded together through the adhesive layer, and both are pressure-bonded or thermocompression-bonded to execute 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 practical use, those that melt in a temperature range of about 80 to 150°C are more preferable. In this case, first, the hot melt resin is melted while considering the melting point of the resin and the viscosity during melting, etc. Then, the melted resin is applied on the knitted or woven fabric or the moisture-permeable waterproof layer and aged while cooling at room temperature to form an adhesive layer. Then, the knitted or woven fabric and the moisture-permeable waterproof layer are bonded together through the adhesive layer and pressure-bonded to execute the second manufacturing method.

[0297] In the manufacturing method, it is preferable to adopt the second manufacturing method. This is because when a moisture-permeable and waterproof layer is laminated using a coating method, there is a concern that pinholes may occur in the moisture-permeable and waterproof layer due to the fine protrusions on the surface of the woven or knitted fabric, and the water pressure resistance tends to decrease. Also, when the woven or knitted fabric is calendered in an attempt to form a uniform moisture-permeable and waterproof layer, there is a concern that the protrusions or the air-retaining layer may be reduced and the desired water repellency cannot be achieved, and a separate inspection of the calender conditions is required, which may complicate the process itself.

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

[0299] · Use of the laminated fabric The laminated fabric is excellent in water repellency and moisture-permeable waterproofness, and the moisture-permeable and waterproof layer does not peel off even in a harsh environment. Therefore, it is suitably used in fields such as outdoor uniforms, sports clothing, and outdoor products.

[0300] [Treatment method] The water-repellent composition of the present disclosure can be applied to a substrate by a conventionally known method as a treatment agent (especially a surface treatment agent). The water-repellent composition in the present disclosure can be dispersed and diluted in an organic solvent or water as necessary, and adhered to the surface of the substrate and dried by a known method such as dip coating, spray coating, foam coating, etc. After drying, a fiber product with the solid component in the water-repellent composition adhered thereto can be obtained. Further, if necessary, it may be applied together with a suitable crosslinking agent and cured. Furthermore, the water-repellent composition of the present disclosure can be used in combination with various additives such as a water-repellent and / or oil-repellent agent, an anti-slip agent, an antistatic agent, a handle modifier, a softener, an antibacterial agent, a flame retardant, a paint fixing agent, an anti-wrinkle agent, a drying rate adjuster, a crosslinking agent, a film-forming aid, a compatibilizer, an antifreezing agent, a viscosity adjuster, an ultraviolet absorber, an antioxidant, a pH adjuster, an insect repellent, an antifoaming agent, etc. Examples of the various additives may be the same as those described as "other components" in the above-mentioned water-repellent composition. The concentration of the non-fluorine copolymer (A) in the treatment agent brought into contact with the substrate may be appropriately changed depending on the use, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0301] [Fiber product] Although various examples can be given as the fiber product as the substrate, for example, fabric products and paper products can be mentioned. The fiber product as the substrate is also referred to as a fiber substrate.

[0302] Examples of fabric products include animal and plant natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or mixed fibers thereof. Fabric products include woven fabrics, knitted fabrics, and non-woven fabrics, fabrics in the form of clothing, and carpets. However, the fibers, yarns, and intermediate fiber products (for example, sliver or roving, etc.) in the state before being made into a fabric may be treated.

[0303] Examples of paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, bleached or unbleached high-yield pulp such as mechanical pulp or thermomechanical pulp, waste paper pulp such as newspaper waste paper, magazine waste paper, cardboard waste paper or deinked waste paper, paper containers made of paper, paper molded articles, etc. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium paper, general liner and core, neutral pure white roll paper, neutral liner, rust-proof liner and metal laminated 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, mold paper (mold container), etc.

[0304] The water repellent composition can be applied to the fiber product (for example, cloth) by any of the methods known for treating the fiber product with a liquid. The fiber product may be immersed in the water repellent composition, or a solution may be attached or sprayed onto the fiber product. The treated fiber product is preferably dried and cured by heating in order to exhibit water repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low temperature heating (for example, 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 fiber product by a cleaning method, for example, it may be applied to the fiber product in a washing application or a dry cleaning method, etc.

[0306] The fiber product to be treated may be cloth, which includes woven fabric (woven cloth), knitted fabric (knitted cloth) and non-woven fabric, cloth in the form of clothing and carpets, etc., but it may also be fiber or yarn or intermediate fiber product (for example, sliver or roving, etc.). The water repellent composition of the present disclosure is particularly effective in making fiber products (for example, synthetic fibers) water repellent.

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

[0308] Examples of natural fibers include cellulose-based fibers such as cotton, linen, pulp, etc., chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as groundwood pulp (GP), pressure rise groundwood pulp (PGW), thermomechanical pulp (TMP), etc., chemical pulps such as softwood unbleached kraft pulp (HNKP; N wood), softwood bleached kraft pulp (NBKP; N wood, NB wood), hardwood unbleached kraft pulp (LUKP; L wood), hardwood bleached kraft pulp (LBKP, L wood), etc., wastepaper pulps such as deinking pulp (DIP), waste pulp (WP), etc., and semi-chemical pulp (CP), etc.

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

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

[0311] "Treatment" means applying the water repellent composition to a substrate by means such as dipping, spraying, coating, etc. By the treatment, the non-fluorine copolymer (A) and the isocyanate derivative (B), which are the active ingredients of the water repellent composition, penetrate into the interior of the substrate and / or adhere to the surface of the substrate. In other words, by the treatment, a substrate (for example, a textile product) to which the non-fluorine copolymer (A) and the isocyanate derivative (B) in the water repellent composition of the present disclosure adhere is obtained.

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

[0313] Examples of the pretreatment of the textile product include cationization treatment by reaction with a reactive quaternary ammonium salt, anionic treatment such as sulfonation, carboxylation, phosphorylation, etc., acetylation treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, polymer coating treatment, etc. after the anionic treatment.

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

[0315] The pretreatment method of the textile product is a monovalent group represented by -SO3M 1 (wherein M 1 represents a monovalent cation), a monovalent group represented by -COOM 2 (wherein M 2 represents a monovalent cation), and -O-P(O)(OX 1 )(OX 2 (wherein X1 and X 2 and X each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms), and a step of imparting at least one functional group selected from the group consisting of monovalent groups (hereinafter, may also be referred to as "specific functional group") may be provided.

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

[0317] The fiber containing the above specific functional group (hereinafter, may also be referred to as "functional group-containing fiber") can be prepared, for example, by the following method. (i) A compound having the above specific functional group is attached to a fiber material. Note that the attachment of the compound may be in a state where a part of the compound and a part of the fiber are chemically bonded within a range where a sufficient amount of the above specific functional group remains. (ii) A fiber in which the above specific functional group is directly introduced into the material constituting the fiber is prepared.

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

[0319] The material of the fiber material is not particularly limited, and examples include natural fibers such as cotton, hemp, 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.), yarns, knitted fabrics (including interlock knitting), woven fabrics (including interweaving), non-woven fabrics, papers, etc.

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

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

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

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

[0324] As the above M 3 , examples include H, K, Na, or an ammonium ion that may have a substituent.

[0325] As the above M 4 , examples include H, K, Na, or an ammonium ion that 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] The above - COOM 2 Examples of the compound having this group 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, etc. as monomers, or a commercially available one can be used.

[0329] Examples of the method for producing a polycarboxylic acid polymer include a method in which a radical polymerization initiator is added to an aqueous solution of the above monomer and / or its salt, and the mixture is heated and reacted at 30 to 150 ° C for 2 to 5 hours. At this time, alcohols such as methanol, ethanol, isopropyl alcohol, etc. or aqueous solvents such as acetone may be added to the aqueous solution of the above monomer and / or its salt. Examples of the radical polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, redox polymerization initiators by combinations of persulfates and sodium bisulfite, hydrogen peroxide, water - soluble azo - type polymerization initiators, etc. These radical polymerization initiators may be used alone or in combination of two or more. Further, during radical polymerization, a chain transfer agent (for example, octyl thioglycolate) may be added for the purpose of adjusting the degree of polymerization.

[0330] In radical polymerization, monomers copolymerizable with the above monomers can be used. Examples of the copolymerizable monomers include vinyl - type monomers such as ethylene, vinyl chloride, vinyl acetate, etc., acrylamide, acrylates, methacrylates, etc. Acrylates and methacrylates preferably 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, propyl methacrylate, etc. These copolymerizable monomers may be used alone or in combination of two or more.

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

[0332] From the viewpoint of obtaining a fiber product with good water repellency, the weight average molecular weight of the polycarboxylic acid polymer is preferably 1000 to 20000, more preferably 3000 to 15000.

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

[0334] The above -O-P(O)(OX 1 )(OX 2 ) Examples of the compound having include, for example, phosphate ester compounds represented by the following general formula.

Chemical formula

[0335] As the above phosphate ester compound, phosphoric acid 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 obtaining a fiber product with good water repellency, it is preferable to use lauryl phosphate ester and decyl phosphate ester.

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

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

[0339] Examples of the method for treating the fiber material with the above pretreatment liquid include padding treatment, dipping treatment, spraying treatment, and coating treatment. As the padding treatment, for example, the method using a padding apparatus described on pages 396 to 397 of the Fiber Dyeing Processing Dictionary (1963, published by Nikkan Kogyo Shimbun) or pages 256 to 260 of Color Dyeing Chemistry III (1975, published by Jitsugyo Publishing Co., Ltd.) can be mentioned. As the coating treatment, for example, the method using a coating machine described on pages 473 to 477 of the General List of Dyeing Finishing Equipment (1981, published by Sen'i Sha) can be mentioned. As the dipping treatment, for example, the method using a batch dyeing machine described on pages 196 to 247 of the General List of Dyeing Finishing Equipment (1981, published by Sen'i Sha) can be mentioned, and a liquid flow dyeing machine, an air flow dyeing machine, a drum dyeing machine, a winch dyeing machine, a washer dyeing machine, a cheese dyeing machine, or the like can be used. As the spraying treatment, for example, an air spray that atomizes the treatment liquid with compressed air and sprays it, or a method using an air spray of a hydraulic atomization method can be mentioned. The treatment conditions such as the concentration of the treatment liquid and the heat treatment after application at this time can be appropriately adjusted in consideration of various conditions such as the purpose and performance. Further, when the pretreatment liquid contains water, it is preferably dried in order to remove the water after adhering it to the fiber material. The drying method is not particularly limited, and either a dry heat method or a wet heat method may be used. The drying temperature is also not particularly limited, but for example, it may be dried at room temperature to 200 °C for 10 seconds to several days. If necessary, heat treatment may be performed at a temperature of 100 to 180 °C for about 10 seconds to 5 minutes after drying.

[0340] In the case where the fiber material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as dyeing. However, when performing reduction scouring, there is a risk that the compound having the above specific functional group adsorbed during the process (for example, a phenolic polymer compound, etc.) may fall off. Therefore, it is preferably carried out after reduction scouring after dyeing.

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

[0342] In the functional group introduction step using the pretreatment liquid, it is preferable to perform the treatment in an amount such that the adhesion amount of the compound having the above specific functional group becomes 1.0 to 7.0 parts by weight with respect to 100 parts by weight of the fiber material. Within this range, high water repellency and texture can be achieved simultaneously at a high level.

[0343] The pretreatment liquid is preferably adjusted to a pH of 3 to 5. For pH adjustment, pH adjusters such as acetic acid and malic acid can be used.

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

[0345] In the functional group introduction step using the pretreatment liquid, it is preferable to remove the compound having the above specific functional group that has been treated in excess. Examples of the removal method include a method using water washing. By performing sufficient removal, it is possible to suppress the inhibition of the expression of water repellency in the subsequent water repellent processing. In addition, the texture of the obtained fiber product becomes good. Further, the obtained functional group-containing fiber is preferably dried sufficiently before contacting with a hydrocarbon-based water repellent.

[0346] (ii) Examples of the fiber in which the above specific functional group is directly introduced into the material constituting the fiber include cation-dyeable polyester (CD-PET).​

[0347] From the viewpoint of improving the water repellency of the resulting fiber product, the zeta potential of the surface of the functional group-containing fiber is preferably -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 and particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

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

Examples

[0349] Hereinafter, the examples of the present disclosure will be specifically described, but the examples do not limit the present disclosure.

[0350] [Water Repellency Test] The water repellency of the test treated cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). The water repellency was evaluated according to the criteria shown below. Note that the larger the score, the better the water repellency.

[0351] 100 No wetting or water droplet adhesion was observed on the surface. 90 The surface was not wet, but adhesion of small water droplets was observed. 80 Wetting on small individual water droplets was observed on the surface. 70 Half of the surface showed wetting, and a state where small individual wetting penetrated the cloth was observed. 50 Wetting was observed on the entire surface. 0 Wetting was observed on the entire surface and the back surface.

[0352] [Washing Durability] For the test cloth, after washing 20 times according to Appendix F C4M of JIS L 1930, the water repellency of the test cloth dried in a tumbler (60 °C for 30 minutes) was evaluated.

[0353] [Slip resistance] The test fabric was tested for warp slippage at a load of 160 N in accordance with ISO 13936-2, and the seam slippage (mm) was measured. The smaller the value of the seam slippage, the better the slip resistance.

[0354] [Preparation of Raw Materials] (Production Example of Aqueous Dispersion Containing Acrylic Polymer) Production Example 1 A 500 ml plastic container was charged with 30 g of a water-soluble glycol-based 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. It was heated to 80 °C, stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed with ultrasonic waves for 15 minutes. Next, this mixture was transferred to a 500 ml autoclave. After nitrogen substitution, 0.2 g of lauryl mercaptan was charged as a chain transfer agent and 1.8 g of vinyl chloride was charged as a copolymerizable monomer. Further, 1 g of an azo group-containing water-soluble initiator was added as a polymerization initiator, the temperature was raised to 60 °C, and the reaction was carried out 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 having a solid content concentration of 30% (specifically, an aqueous dispersion containing a hydrocarbon-based water-repellent resin, a surfactant, and a liquid medium).

[0355] Production Examples 2 to 8 An aqueous dispersion containing an acrylic polymer, a surfactant, and a liquid medium was prepared in the same manner as in Production Example 1 except that the formulation was changed according to Table 1.

[0356]

Table 1

[0357] (Production Example of Aqueous Dispersion Containing Polyurethane) Production Example 9 1. Synthesis of Aliphatic Polyisocyanate Derivative In a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser, under a nitrogen atmosphere, 500 parts by mass of 1,6 - hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, trade name: Takenate 700), 0.25 parts by mass of 2,6 - di(tert - butyl)-4 - methylphenol (alias: dibutylhydroxytoluene, BHT, hindered phenol - type antioxidant), and 0.25 parts by mass of tetraphenyl - dipropylene glycol - diphosphite (organic phosphite ester, co - catalyst) were mixed. Then, 10.7 parts by mass of 1,3 - butanediol was added to this mixture, and nitrogen was introduced into its liquid phase for 1 hour. Thereafter, the mixture was heated to 80°C and reacted for 3 hours, and then cooled to 60°C. Then, 0.2 parts by mass of trimethyl - N - 2 - hydroxypropylammonium 2 - ethylhexanoate was added as an isocyanuration catalyst and reacted for 1.5 hours. Then, 0.04 parts by mass of o - toluenesulfonamide was added to 100 parts by mass of HDI. Then, this reaction mixture was passed through a thin - film distillation apparatus (temperature 150°C, vacuum degree 93.3 Pa) and distilled until the amount of residual HDI monomer became 0.5% or less to obtain an aliphatic polyisocyanate derivative (isocyanurate derivative of hexamethylene diisocyanate). The isocyanate - group content of the obtained aliphatic polyisocyanate derivative was 20.9%, and the average number of isocyanate functional groups was 3.0.

[0358] 2. Production of Hydrocarbon - based Polyurethane Into a reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, 100.20 g of the above - mentioned aliphatic polyisocyanate derivative, 67.60 g of Calcohol 8098 (stearyl alcohol, manufactured by Kao Corporation), and 22.30 g of oleyl alcohol as long - chain active hydrogen compounds were mixed, and reacted at 110°C under a nitrogen atmosphere for 4 hours until the concentration of isocyanate groups reached 3.67%. Next, the reaction solution was cooled to 80°C, 9.90 g of N - methyldiethanolamine was added as a cationic active hydrogen compound, and reacted at 80°C for 1 hour. Next, 50.00 g of methyl ethyl ketone was added as a solvent, and the reaction was carried out at 80 °C until it was confirmed by infrared absorption spectrum that the isocyanate group had disappeared. Next, 57.69 g of methyl ethyl ketone was added to the reaction solution, the temperature was raised to 80 °C, and the mixture was stirred until the reaction solution was completely dissolved, and then cooled to 75 °C. Then, 18.96 g of acetic acid was added as an acid compound for neutralization. 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). Next, the solvent was removed with an evaporator under reduced pressure at a water bath temperature of 60 °C until the solid content concentration reached 20% by weight or more. Next, a water dispersion containing polyurethane was obtained by adjusting with ion-exchanged water so that the solid content concentration excluding the acid compound (acetic acid) was 20% by weight.

[0359] Production Example 10 116 g of sorbitan tristearate and 150 g of 4-methyl-2-pentanone (MIBK) were charged into a 500 mL four-necked flask equipped with a stirrer, a thermometer, and a reflux tube. Next, in order to remove excess water vapor from this mixed solution, while maintaining the temperature of the mixed solution at 70 °C, the mixed solution was stirred, the mixed solution was refluxed for 1 hour, and then allowed to cool to 50 °C. Then, while maintaining stirring, 30 g of Desmodur N-100 (biuret derivative of hexamethylene diisocyanate, Covestro) was added dropwise to the mixed solution with a dropping funnel. After completion of the dropwise addition, 1 drop of dibutyltin dilaurate was added as a catalyst, and the reaction was carried out at 80 °C for 1 hour. Next, 25 g of sorbitan monostearate was added, and the reaction was further carried out at 80 °C for 4 hours. Next, after cooling to 60 °C, the reaction solution was recovered, and the reaction solution was slowly mixed with 60 °C water containing an arbitrary amount of cationic emulsifier and polyoxyethylene alkyl ether. The mixed solution was stirred at 6000 rpm for 1 minute using a homomixer and then emulsified and dispersed with ultrasonic waves for 15 minutes. Then, after removing the solvent (MIBK) by a vacuum operation, pure water was added to adjust the concentration, and a water dispersion containing 20% solid content of polyurethane was obtained.

[0360] Production Example 11 Into a 500 mL four-necked flask equipped with a stirrer, a thermometer, and a reflux tube, 150 g of methyl ethyl ketone (MEK) and 51 g of stearyl alcohol were charged. Next, in order to remove the excess water vapor of this mixture, while maintaining the temperature of the mixture at 70 °C, the mixture was stirred, the mixture was refluxed for 1 hour, and then allowed to cool to 50 °C. Then, 30 g of Desmodur N3200A (a biuret derivative of hexamethylene diisocyanate, manufactured by Covestro) was added to the mixture, and further reacted at 80 °C for 4 hours. Next, after cooling to 60 °C, the reaction solution was recovered, and the reaction solution was slowly admixed with water at 60 °C containing an arbitrary amount of polyoxyethylene alkyl ether. This admixed solution was stirred with a homomixer at 6000 rpm for 1 minute and then emulsified and dispersed with ultrasonic waves for 15 minutes. Next, after removing the solvent (MEK) by a vacuum operation, pure water was added to adjust the concentration, and an aqueous dispersion containing 20% solid content of polyurethane was obtained.

[0361] (Production Example of Aqueous Dispersion Containing Silicone) Production Example 12 Into a 200 mL four-necked flask equipped with a stirrer, a thermometer, and a reflux tube, 12 g of methylhydrogen silicone oil (SiH:SiCH3 molar ratio = 50:50 measured by 1H NMR) and 0.02 g of a platinum catalyst were charged. Next, 36 g of 1-hexacosene was charged into a dropping funnel, and 1-hexacosene was dropped from the dropping funnel while maintaining the temperature at 70 °C. After completion of the dropping, the reaction was further carried out at 70 °C for 3 hours. It was confirmed by infrared spectroscopy (IR) that the peak of SiH disappeared, and 47 g of a solid silicone polymer was obtained. Next, 28 g of a silicone polymer, 5.6 g of a water-soluble glycol-based 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 a cationic emulsifier were charged into a 250-ml glass container, heated to 75°C, stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed with ultrasonic waves for 10 minutes to obtain an aqueous dispersion of the silicone polymer. Thereafter, pure water was added to prepare an aqueous dispersion of the silicone polymer with a solid content concentration of 30% by weight.

[0362] (Production Example of Aqueous Dispersion Containing Wax) Production Example 13 150 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 reaction vessel, sealed, heated to 110 - 120°C with stirring, and then subjected to high-pressure emulsification under high pressure for 30 minutes to prepare an aqueous dispersion of the wax. Thereafter, pure water was added to prepare an aqueous dispersion of the wax with a solid content of 30% by weight.

[0363] Production Example 14 150 g of oxidized polypropylene wax with a melting point of 150°C, an acid value of 44 mg KOH / g, and a density of 0.93, 325 g of ion-exchanged water, 25 g of a surfactant with an HLB of 15, and 5 g of a 48% aqueous potassium hydroxide solution were placed in a reaction vessel, sealed, heated to 160°C with stirring, subjected to high-pressure emulsification under high pressure for 1 hour, and then cooled to 90°C to obtain an aqueous dispersion of the polypropylene wax. Thereafter, pure water was added to prepare an aqueous dispersion of the polypropylene wax with a solid content of 30% by weight.

[0364] [Examples 1 to 13, Comparative Examples 1 to 3] The above-mentioned aqueous dispersion and the hydrophilic particles shown in Table 2 (average primary particle diameter 25 nm, zeta potential +45 mV, turbidity 2.0 ppm) were added and mixed to obtain an aqueous dispersion with a solid content concentration of 30% according to the composition weight ratio shown in Table 2. This aqueous dispersion was diluted with tap water to prepare 1000 g of a test solution with a solid content concentration of 1.0% by weight. Next, after impregnating a test cloth (polyester fabric, nylon fabric) with this test solution, it was passed through a mangle, passed through a pin tenter at 160°C for 1 minute, dried, and cured, and the above-mentioned test was conducted.

[0365] [Example 14] The above-mentioned aqueous dispersion and the antibacterial and antifungal agent shown in Table 2 (benzisothiazolin-3-one 75 ppm, and a mixture of 5-chloro-2-methyl-2H-isothiazol-3-one and 2-methyl-2H-isothiazol-3-one (weight ratio 3:1) 75 ppm) were added and mixed to obtain an aqueous dispersion with a solid content concentration of 30% according to the composition weight ratio shown in Table 2. This aqueous dispersion was diluted with tap water to prepare 1000 g of a test solution with a solid content concentration of 1.0% by weight. Next, after impregnating a test cloth (polyester fabric, nylon fabric) with this test solution, it was passed through a mangle, passed through a pin tenter at 160°C for 1 minute, dried, and cured, and the above-mentioned test was conducted.

[0366]

Table 2

[0367] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims.

Claims

1. A non-fluorine copolymer (A) containing a repeating unit derived from a hydrophobic monomer (a1) having a hydrocarbon group with 2 to 40 carbon atoms, and a repeating unit derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride, and an isocyanate derivative (B), In the non-fluorine copolymer (A), the amount of the repeating unit derived from the monomer (a2) is 1 to 15% by weight based on the total of the amount of the repeating unit derived from the monomer (a1) and the amount of the repeating unit derived from the monomer (a2). A water repellent composition.

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

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

4. The isocyanate derivative (B) has an alkyl group having 12 or more and 30 or less carbon atoms. The water repellent composition according to claim 1.

5. The isocyanate derivative (B) is polyurethane. The water repellent composition according to claim 1.

6. The isocyanate derivative (B) is a compound obtained by reacting at least one active hydrogen compound selected from the group consisting of hydrocarbon alcohols, sugar alcohol modified products, and hydroxy acid modified products with at least one raw material isocyanate selected from the group consisting of acyclic aliphatic polyisocyanates and derivatives thereof. The water repellent composition according to claim 1.

7. The water repellent composition according to claim 1, containing silicone.

8. The amount of the silicone is 0.1 part by weight to 20 parts by weight per 100 parts by weight of the non-fluorine copolymer (A). The water repellent composition according to claim 7.

9. In the non-fluorine copolymer (A), the amount of the repeating unit derived from the monomer (a2) is 1 to 9% by weight based on the total of the amount of the repeating unit derived from the monomer (a1) and the amount of the repeating unit derived from the monomer (a2). The water repellent composition according to claim 1.

10. The amount of the isocyanate derivative (B) is 0.1 part by weight to 20 parts by weight per 100 parts by weight of the non-fluorine copolymer (A). The water repellent composition according to claim 1.

11. The hydrophobic monomer (a1) has the formula: CH ２ =C(-R １２ )-C(=O)-Y １１ -(R １１ ) ｋ [In the formula, R １１ is a hydrocarbon group having 2 to 40 carbon atoms, R １２ is a hydrogen atom, a monovalent organic group or a halogen atom, Y １１ is a divalent to tetravalent group having 1 carbon atom and being directly bonded, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ -, and -NR'- (R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), and is a divalent to tetravalent group composed of at least one selected therefrom, k is from 1 to 3. It is a compound represented by The isocyanate derivative (B) has an alkyl group having 12 to 30 carbon atoms and is a compound obtained by reacting at least one active hydrogen compound selected from the group consisting of hydrocarbon alcohols, sugar alcohol modified products, and hydroxy acid modified products with at least one raw material isocyanate selected from the group consisting of acyclic aliphatic polyisocyanates and their derivatives. The water repellent composition according to claim 1, wherein the amount of the isocyanate derivative (B) is 0.1 part by weight to 20 parts by weight per 100 parts by weight of the non-fluorine copolymer (A).

12. The hydrophobic monomer (a1) has the formula: CH ２ =CH-C(=O)-Y １１ -R １１ [In the formula, R １１ is an alkyl group having 12 to 25 carbon atoms, Y １１ is -O- or -O-(CH ２ ) m -NH-C(=O)-, and m is an integer of 2 or 4.] It is a compound represented by The chloride monomer (a2) is vinyl chloride. The isocyanate derivative (B) is A compound obtained by reacting a hydrocarbon alcohol having an alkyl group having 12 to 25 carbon atoms with an isocyanurate derivative of an acyclic aliphatic polyisocyanate having an aliphatic hydrocarbon group having 2 to 10 carbon atoms or A compound obtained by reacting a sorbitan modified product modified with an alkyl group having 12 to 25 carbon atoms with a biuret derivative of an acyclic aliphatic polyisocyanate having an aliphatic hydrocarbon group having 2 to 10 carbon atoms. The water repellent composition according to claim 1, wherein the amount of the isocyanate derivative (B) is 1 part by weight to 10 parts by weight per 100 parts by weight of the non-fluorine copolymer (A).

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

14. Before applying the water repellent composition to the fiber substrate, to the fiber -SO ３ M １ (wherein M １ represents a monovalent cation) a monovalent group represented by -COOM ２ (wherein M ２ represents a monovalent cation), a monovalent group represented thereby, and -O-P(O)(OX １ )(OX ２ )(wherein X １ and X ２ each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms), and the method for producing a fiber product according to claim 13, comprising a step of imparting one or more functional groups selected from the group consisting of monovalent groups represented by

15. A fiber product to which the non-fluorine copolymer (A) and the isocyanate derivative (B) in the water repellent composition according to any one of claims 1 to 12 are attached.

16. -SO ３ M １ (wherein M １ represents a monovalent cation) represents a monovalent group, -COOM ２ (wherein M ２ represents a monovalent cation) and a monovalent group represented by, and -O-P(O)(OX １ )(OX ２ )(wherein X １ and X ２ each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms), and a fiber product according to claim 15, to which one or more functional groups selected from the group consisting of monovalent groups represented by are attached.

Images