Dispersion

Abstract

To provide a novel dispersion that demonstrates product stability and water repellency.SOLUTION: A dispersion contains: a non-fluorine copolymer (A) which comprises 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 a liquid medium (B) which comprises a water-soluble organic solvent (b1) having at least two groups selected from the group consisting of hydroxy groups and ether groups. The concentration of an unreacted chloride monomer (a2) is 10.0 ppm or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to a dispersion. [Background technology]

[0002] It is known that by using a water-dispersible water- and oil-repellent agent comprising a copolymer obtained by copolymerizing a polyfluoroalkyl group-containing monomer, vinyl chloride or vinylidene chloride, and other copolymerizable monomers, and having an unreacted vinyl chloride monomer or vinylidene chloride monomer concentration of 10 ppm or less, it is possible to provide a water- and oil-repellent agent with excellent storage stability that reduces problems such as changes in the form of the water- and oil-repellent agent and deterioration of its performance (Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 4-80218 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, when using non-fluorinated copolymers instead of fluorinated polymers such as those described in Patent Document 1, the product stability and water repellency are insufficient. The object of this disclosure is to provide a novel dispersion that can achieve both product stability and water repellency. [Means for solving the problem]

[0005] One embodiment of this disclosure is as follows: [Section 1] A non-fluorinated copolymer (A) comprising repeating units derived from a hydrophobic monomer (a1) having a hydrocarbon group having 2 to 40 carbon atoms, and repeating units derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride, The liquid medium (B) comprises a water-soluble organic solvent (b1) having at least two groups selected from the group consisting of hydroxyl groups and ether groups, A dispersion in which the concentration of unreacted chloride monomer (a2) is 10.0 ppm or less. [Section 2] The dispersion according to claim 1, wherein the hydrocarbon group in the hydrophobic monomer (a1) is a linear alkyl group having 10 or more carbon atoms. [Section 3] The hydrophobic monomer (a1) is given by formula: CH2=C(-R 12 )-C(=O)-Y 11 -(R 11 ) k [In the formula, R 11 It is a hydrocarbon group having 2 to 40 carbon atoms. R 12 is a hydrogen atom, a monovalent organic group, or a halogen atom. Y 11 It is a 2-4 valent group composed of at least one directly bonded, 2-4 valent hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2- and -NR'- (where R' is a hydrogen atom or a hydrocarbon group having 1-4 carbon atoms), k is between 1 and 3. A dispersion according to item 1 or 2, which is a compound represented by [the specified compound]. [Section 4] The dispersion according to any one of claims 1 to 3, wherein the hydrophobic monomer (a1) comprises repeating units derived from a hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group. [Section 5] The dispersion according to any one of claims 1 to 4, wherein the copolymer (A) further comprises repeating units derived from a cyclic hydrocarbon group-containing monomer (a3). [Section 6] The dispersion according to any one of claims 1 to 5, wherein the copolymer (A) further comprises repeating units derived from a crosslinkable monomer (a4). [Section 7] The amount of repeating units derived from the hydrophobic monomer (a1) is 20% by weight or more in the copolymer (A), The dispersion according to any one of claims 1 to 6, wherein the amount of repeating units derived from the chloride monomer (a2) in the copolymer (A) is 80% by weight or less. [Section 8] A dispersion that is an aqueous dispersion, as described in any one of items 1 to 7. [Section 9] The dispersion according to any one of claims 1 to 8, wherein the water-soluble organic solvent (b1) is a glycol compound or its monoalkyl ether. [Section 10] The dispersion according to any one of claims 1 to 9, wherein the amount of the water-soluble organic solvent (b1) is 5 parts by weight or more and 80 parts by weight or less per 100 parts by weight of the copolymer (A). [Section 11] The dispersion according to any one of items 1 to 10, wherein the concentration of the unreacted chloride monomer (a2) is 5.0 ppm or less. [Section 12] Step (i) of copolymerizing a hydrophobic monomer (a1) and at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride in a polymerization solvent to obtain a polymer solution containing a non-fluorine copolymer (A), and (ii) A step to reduce the concentration of the unreacted chloride monomer (a2) in the obtained polymer solution to 10.0 ppm or less. Includes, The polymerization solvent contains a water-soluble organic solvent (b1), or the water-soluble organic solvent (b1) is added to the polymer solution. A method for producing a dispersion, wherein the water-soluble organic solvent (b1) has at least two groups selected from the group consisting of hydroxyl groups and ether groups. [Section 13] A water-repellent agent that is a dispersion described in any one of items 1 to 11. [Section 14] A method for producing a processed product, comprising the step of applying a dispersion liquid described in any one of items 1 to 11 to a substrate. [Section 15] A textile product to which any of the dispersions described in items 1 to 11 has been applied. [Effects of the Invention]

[0006] The dispersions in this disclosure exhibit excellent product stability and water repellency. Furthermore, treating products with the dispersions in this disclosure can improve the usability and durability of the products, including chalk mark resistance and friction fastness. [Modes for carrying out the invention]

[0007] <Dispersion> The dispersions (especially aqueous dispersions) in this disclosure are Non-fluorinated copolymer (A), and Liquid medium (B) The dispersion further comprises the following: Surfactants, and / or hardening agent It may contain [the specified component]. The dispersion may further contain other components. The dispersion does not have to contain fluorine-containing compounds.

[0008] [Non-fluorine copolymer (A)] The non-fluorinated copolymer (A) does not contain fluorine atoms.

[0009] Non-fluorinated copolymer (A) is, Repeating units derived from hydrophobic monomer (a1), and Repeating units derived from chloride monomer (a2) It includes. The non-fluorine copolymer (A) further Cyclic hydrocarbon group-containing monomer (a3), and / or Crosslinkable monomer (a4) It may also contain. The non-fluorine copolymer (A) may also contain other monomers (a5).

[0010] (Hydrophobic monomer (a1))

[0011] The hydrophobic monomer (a1) has one ethylenically unsaturated double bond and a hydrocarbon group having 2 to 40 carbon atoms.

[0012] 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.

[0013] The hydrophobic monomer (a1) is of 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 valence, -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.] and may be a monomer represented by.

[0014] R 11The hydrocarbon group is preferably a branched or linear (preferably a long-chain linear) hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, and especially an alkyl group. The -CH3 group has a lower surface free energy than -CH2- and tends to exhibit liquid repellency. For this reason, a structure with many branches and many -CH3 groups is preferred. On the other hand, a long-chain alkyl group of a certain length exhibits high liquid repellency due to its crystallinity. Therefore, it may be a branched hydrocarbon group (for example, a branched alkyl group), especially a t-butyl group or isopropyl group, a highly branched group, or a long-chain hydrocarbon group (or a long-chain linear hydrocarbon group), for example, an alkyl group. 11 The number of carbon atoms may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 11 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and preferably 10 or more. 11 The number of carbon atoms may be 40 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 12 or less.

[0015] k is 1, 2, or 3. 11 When it has a tetravalent hydrocarbon group with 1 carbon atom, k=3. 11 When it has a trivalent hydrocarbon group with 1 carbon atom, k=2. 11 If it does not have trivalent and tetravalent carbon-1 hydrocarbon groups (for example, Y 11 k=1 when it has a divalent 1-carbon hydrocarbon group (-CH2-) (for example, 1 to 6 of them).

[0016] R 12 This may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Alternatively, it may be a -CF3 group. 12 Examples include hydrogen atoms, methyl groups, chlorine atoms, bromine atoms, iodine atoms, fluorine atoms, -CF3 groups, and cyano groups. 12 R is preferably a hydrogen atom, a methyl group, or a chlorine atom. 12 It is more preferable that it be a methyl group. 12 The presence of a methyl group provides higher liquid repellency. 12This can be a hydrogen atom, especially from the standpoint of reactivity.

[0017] Y 11 It is preferable that the group is divalent. Examples of divalent to tetravalent hydrocarbon groups with 1 carbon atom include -CH2-, -CH= with a branched structure, and -C≡ with a branched structure.

[0018] Y 11 -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-X'-, -Y'-X'-Y'- , -Y'-X'-Y'-C(=O)-, -Y'-X'-C(=O)-Y'-, -Y'-X'-Y'-C(=O)-Y'-, or -Y'-X'-Y'-X'- [In the formula, Y' is independently a direct bond, -O-, -NR'- (where R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), or -S(=O)2-. X' is -(CH2) m -(m is an integer from 1 to 5), a linear hydrocarbon group having an unsaturated bond with 1 to 5 carbon atoms, a branched hydrocarbon group having 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l -(l is an independent integer between 0 and 5, and -C6H4- is a phenylene group). It's fine to be that way. Y 11 It is preferable that the group is not solely composed of divalent hydrocarbon groups.

[0019] Y 11 Specific examples are -O-, -NH-, -OC(=O)-, -NH-C(=O)-, -OC(=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 -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2)m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2-, -NH-(CH2) m -S(=O)2-NH--NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, or -NH-(CH2) m -NH-C6H4- [where m is an integer from 1 to 5, especially 2 or 4].

[0020] 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 -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -NH-C(=O)-NH- [In the formula, m is an integer between 1 and 5, in particular 2 or 4.] It is preferable that this is the case. 11 is -O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, or -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, especially -O-(CH2) m -NH-C(=O)- is more preferable.

[0021] The hydrophobic monomer (a1) is preferably free of reactive or hydrophilic groups. Examples of reactive groups include epoxy groups, chloromethyl groups, bromomethyl groups, iodomethyl groups, isocyanate groups, and blocked isocyanate groups. Examples of hydrophilic groups include hydroxyl groups, polyalkylene oxide groups, amino groups, carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, alkali metal or alkaline earth metal bases of carboxylic acids, sulfonic acids, phosphoric acid, chlorine or bromine, ammonium bases with iodide ions as counteranions, and other ionic groups. Here, reactive groups and hydrophilic groups may overlap.

[0022] The hydrophobic monomer (a1) may have a water solubility of 10 g / l or less, 5 g / l or less, 3 g / l or less, 1 g / l or less, 0.5 g / l or less, or 0.1 g / l or less at 25°C, and preferably 3 g / l or less. The homopolymer of the hydrophobic monomer (a1) may have a water solubility of 10 g / l or less, 5 g / l or less, 3 g / l or less, 1 g / l or less, 0.5 g / l or less, or 0.1 g / l or less at 25°C, and preferably 3 g / l or less.

[0023] 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 of the copolymer, particularly water repellency. The water contact angle of the homopolymer may be a value obtained by spin-coating a chloroform solution having a solid content concentration of 1.0% of the homopolymer on a silicon wafer substrate, dropping 2 μL of water onto the coating film, and measuring the contact angle 1 second after the droplet adheres.

[0024] Specific examples of the hydrophobic monomer (a1) are as follows. The compounds represented by 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 m H 2m NHC(=O)C n H 2n+1 CH2=CHC(=O)OC(=O)NHC n H 2n+1 CH2=CHC(=O)OC2H4NHC(=O)OC n H 2n+1 CH2=CHC(=O)OC2H4NHC(=O)NHC n H2n+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 TIFF2023178300000001.tif2966 TIFF2023178300000002.tif3069CH2=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.] TIFF2023178300000003.tif3142

[0025] 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.

[0026] From the viewpoint of the liquid-repellent properties of the dispersion, it is preferable that the hydrophobic monomer (a1) includes 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) without an amide group, a urea group, or a urethane group is also acceptable. An example of a hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group is CH2=C(-R 12 )-C(=O)-O-(CH2) m -NH-C(=O)-R 11 CH2=C(-R 12 )-C(=O)-O-(CH2) m -OC(=O)-NH-R 11 CH2=C(-R 12 )-C(=O)-O-(CH2) m -NH-C(=O)-OR 11 , and CH2=C(-R 12 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R 11 Examples include the hydrophobic monomer (a1), CH2=C(-R 12 )-C(=O)-O-(CH2) m -NH-C(=O)-R 11 It may include.

[0027] (Chloride monomer (a2)) The non-fluorinated copolymer (A) contains repeating units derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride. The chloride monomer (a2) is preferably vinyl chloride.

[0028] (Cyclic hydrocarbon group-containing monomer (a3)) The non-fluorinated copolymer (A) may have repeating units derived from a cyclic hydrocarbon group-containing monomer (a3). The cyclic hydrocarbon group-containing monomer (a3) ​​is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.

[0029] The cyclic hydrocarbon group-containing monomer (a3) ​​preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0030] The cyclic hydrocarbon group may be aliphatic or aromatic, and is preferably aliphatic. The cyclic hydrocarbon group may be saturated or unsaturated, and is preferably saturated. The cyclic hydrocarbon group may be monocyclic, polycyclic, or crosslinked, and is preferably a crosslinked. The cyclic hydrocarbon group may have a chain-like group (for example, a linear or branched hydrocarbon group).

[0031] The number of carbon atoms in the cyclic hydrocarbon group may be 4 or more, 6 or more, or 8 or more, and may be 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less.

[0032] Specific examples of cyclic hydrocarbon groups include cyclohexyl group, t-butylcyclohexyl group, adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, bornyl group, isobornyl group, norbornyl group, dicyclopentanyl group, dicyclopentenyl group, benzyl group, phenyl group, naphthyl group, 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (e.g., cyclohexylene group, adamantylene group, phenylene group, naphthylene group, etc.), and substituted groups thereof.

[0033] Specific examples of cyclic hydrocarbon group-containing monomers (a3) ​​include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and compounds obtained by substituting these acrylates with acrylamide. These may be used alone or in combination of two or more.

[0034] (Cross-linkable monomer (a4)) The non-fluorinated copolymer (A) may have repeating units derived from the crosslinkable monomer (a4). The crosslinkable monomer (a4) is a monomer capable of imparting crosslinkability to the copolymer and may have at least two selected from the group consisting of a reactive group and an olefinic carbon-carbon double bond. The crosslinkable monomer (a4) may be a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group.

[0035] The crosslinkable monomer (a4) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0036] Examples of reactive groups include hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, carbonyl groups, and isocyanate groups (blocked isocyanate groups).

[0037] Specific examples of crosslinkable monomers (a4) include diacetone(meth)acrylamide, N-methylol(meth)acrylamide, hydroxyethyl(meth)acrylamide, glycidyl(meth)acrylate, hydroxymethyl(meth)acrylate, hydroxyethyl(meth)acrylate, 2,3-dihydroxypropyl(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, 2-acetoacetoxyethyl(meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and compounds obtained by substituting these acrylates with acrylamide. These may be used alone or in combination of two or more. These may be used individually or in combination of two or more.

[0038] (Other monomers (a5)) ) The non-fluorinated copolymer (A) may contain repeating units derived from monomers (a1) to (a4) other than monomer (a5).

[0039] Other specific examples of monomers (a5) include, for example, ethylene, halogenated olefins, vinyl acetate, acrylonitrile, alkoxypolyalkylene glycol (meth)acrylate, and vinyl alkyl ethers. Other non-fluorinated monomers are not limited to these examples. These may be used alone or in combination of two or more.

[0040] (Composition of polymer) The amount of repeating units derived from the hydrophobic monomer (a1) may be 15% by weight or more, 20% by weight or more, 25% by weight or more, 35% by weight or more, 45% by weight or more, 55% by weight or more, or 65% by weight or more, relative to the nonfluorine copolymer (A). The amount of repeating units derived from the hydrophobic monomer (a1) may be 98% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less, relative to the nonfluorine copolymer (A).

[0041] The proportion of hydrophobic monomers (a1) having an amide group, a urea group, or a urethane group among the repeating units derived from the hydrophobic monomer (a1) may be 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, or 75% by weight or more. The proportion of hydrophobic monomers (a1) having an amide group, a urea group, or a urethane group among the repeating units derived from the hydrophobic monomer (a1) may be 100% by weight or less, 90% by weight or less, 80% by weight or less, or 70% by weight or less.

[0042] The amount of repeating units derived from the chloride monomer (a2) may be 3% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, or 20% by weight or more, 25% by weight or more, or 35% by weight or more, relative to the nonfluorine copolymer (A). The amount of repeating units derived from the chloride monomer (a2) may be 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less, relative to the nonfluorine copolymer (A), and is preferably 60% by weight or less.

[0043] The amount of repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, relative to the non-fluorinated copolymer (A). The amount of repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​may be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, or 5% by weight or less, relative to the non-fluorinated copolymer (A).

[0044] The amount of repeating units derived from the crosslinkable monomer (a4) may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, relative to the nonfluorine copolymer (A). The amount of repeating units derived from the crosslinkable monomer (a4) may be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, or 5% by weight or less, relative to the nonfluorine copolymer (A).

[0045] The amount of repeating units derived from other monomers (a5) may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, relative to the nonfluorine copolymer (A). The amount of repeating units derived from other monomers (a5) may be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less, relative to the nonfluorine copolymer (A).

[0046] The amount of repeating units derived from chloride monomer (a2) may be 5 parts by weight or more, 10 parts by weight or more, 25 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of repeating units derived from hydrophobic monomer (a1). The amount of repeating units derived from chloride monomer (a2) may be 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, or 25 parts by weight or less, per 100 parts by weight of repeating units derived from hydrophobic monomer (a1).

[0047] The amount of repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​may be 2.5 parts by weight or more, 5 parts by weight or more, 12.5 parts by weight or more, 25 parts by weight or more, 35 parts by weight or more, or 45 parts by weight or more, per 100 parts by weight of repeating units derived from the hydrophobic monomer (a1). The amount of repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​may be 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per 100 parts by weight of repeating units derived from the hydrophobic monomer (a1).

[0048] The amount of repeating units derived from the crosslinkable monomer (a4) may be 2.5 parts by weight or more, 5 parts by weight or more, 12.5 parts by weight or more, 25 parts by weight or more, 35 parts by weight or more, or 45 parts by weight or more, per 100 parts by weight of repeating units derived from the hydrophobic monomer (a1). The amount of repeating units derived from the crosslinkable monomer (a4) may be 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per 100 parts by weight of repeating units derived from the hydrophobic monomer (a1).

[0049] The amount of repeating units derived from other monomers (a5) may be 2.5 parts by weight or more, 5 parts by weight or more, 12.5 parts by weight or more, 25 parts by weight or more, 35 parts by weight or more, or 45 parts by weight or more, per 100 parts by weight of repeating units derived from hydrophobic monomer (a1). The amount of repeating units derived from other monomers (a5) may be 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per 100 parts by weight of repeating units derived from hydrophobic monomer (a1).

[0050] The total amount of repeating units derived from the hydrophobic monomer (a1), the chloride monomer (a2), and the hydrocarbon group-containing monomer (c) may be 75% or more by weight, 80% or more by weight, 85% or more by weight, 90% or more by weight, or 95% or more by weight relative to the nonfluorine copolymer (A).

[0051] [Unreacted chloride monomer (a2)] The unreacted chloride monomer (a2) is at least one selected from the group consisting of vinyl chloride and vinylidene chloride.

[0052] [Liquid media (B)] The dispersion contains a liquid medium (B). The liquid medium (B) contains a water-soluble organic solvent (b1). The liquid medium (B) may be a mixture of the water-soluble organic solvent (b1) and water. The liquid medium (B) may further contain other solvents.

[0053] The water-soluble organic solvent (b1) is a water-soluble organic solvent having at least two groups selected from the group consisting of hydroxyl groups and ether groups. The water-soluble organic solvent (b1) is preferably aliphatic, and may be, for example, a linear aliphatic group. The water-soluble organic solvent (b1) may also be a compound consisting only of carbon atoms, hydrogen atoms, and oxygen atoms. By including the water-soluble organic solvent (b1), the feel and durability of the product treated with the dispersion can be improved. For example, issues such as dye bleeding, decreased heat resistance, and decreased friction fastness can be improved.

[0054] The water-soluble organic solvent (b1) preferably has at least one hydroxyl group. The water-soluble organic solvent (b1) preferably has one hydroxyl group and at least one group selected from hydroxyl groups and ether groups. The number of hydroxyl groups in the water-soluble organic solvent (b1) may be 1 or more, 2 or more, 3 or more, or 4 or more, and may be 5 or less, 4 or less, 3 or less, or 2 or less, for example, 1 (monool), 2 (diol), or 3 (triol). The water-soluble organic solvent (b1) may or may not have an ether group. The number of ether groups in the water-soluble organic solvent (b1) may be 1 or more, 2 or more, 3 or more, or 4 or more, and may be 5 or less, 4 or less, 3 or less, or 2 or less, for example, 1 (monoether), 2 (diether), or 3 (triether). The water-soluble organic solvent (b1) may be a glycol compound or its monoalkyl ether form.

[0055] The boiling point of the water-soluble organic solvent (b1) may be 100°C or higher, 120°C or higher, 140°C or higher, 160°C or higher, 180°C or higher, 200°C or higher, 220°C or higher, 240°C or higher, or 260°C or higher, preferably 140°C or higher, more preferably 180°C or higher. The boiling point of the water-soluble organic solvent (b1) may be 425°C or lower, 400°C or lower, 375°C or lower, 350°C or lower, 325°C or higher, 300°C or lower, 275°C or lower, 250°C or lower, 225°C or lower, or 200°C or lower, preferably 350°C or lower.

[0056] The solubility of the water-soluble organic solvent (b1) at 25°C (g / 100g) may be 50 or more, 70 or more, 100 or more, or infinite (miscible with water), preferably 100 or more, more preferably infinite (miscible with water). The solubility of the water-soluble organic solvent (b1) at 25°C (g / 100g) may be 200 or less, or 150 or less.

[0057] Specific examples of water-soluble organic solvents (b1) include glycols which are monomers, oligomers, or polyalkylene glycols or thioglycols having (C2-C6) alkylene units, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, pentamethylene glycol, 1,6-hexylene glycol, 1,2-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, and dithiodiglycol; polyols such as glycerin and hexane-1,2,6-triol (especially triols); and (C1-C4) alkyl ethers (preferably monoethers, diethers) of polyhydric alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), or triethylene glycol monomethyl ether or triethylene glycol monoethyl ether. These may be used individually or in combination of two or more.

[0058] Other solvents may include esters (e.g., esters with 2 to 30 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 30 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols with 1 to 30 carbon atoms, specifically isopropyl alcohol), ethers, alkanes, toluene-based solvents, and carbon halides. Specific examples of other solvents include acetone, isopropyl alcohol, chloroform, HCHC225, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and mixtures thereof. These may be used individually or in combination of two or more.

[0059] The liquid medium (B) may be a polymerization solvent for carrying out the polymerization reaction. The liquid medium (B) may also be prepared by adding each solvent after polymerization. For example, monomers may be polymerized in the presence of an organic solvent to produce a non-fluorine copolymer (A), and then water may be added, followed by the removal of the organic solvent if necessary.

[0060] [Surfactants] The dispersion may contain a surfactant if it is an aqueous dispersion. The surfactant may include at least one of a nonionic surfactant, a cationic surfactant, and an anionic surfactant. Furthermore, the surfactant may also include an amphoteric surfactant. Alternatively, the dispersion may not contain a surfactant. Generally, the dispersion contains a surfactant if it is an aqueous dispersion. The surfactant may be added before or after polymerization, or it may not be added. Even without adding a surfactant, an aqueous dispersion can be obtained in an aqueous medium due to the properties of the non-fluorine copolymer (A) itself.

[0061] Nonionic surfactants are nonionic surfactants having an oxyalkylene group. The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of a nonionic surfactant is generally preferably 2 to 100. Nonionic surfactants may be alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycol esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene oxide adducts of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide adduct and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (which may be random copolymers or block copolymers) are preferred. Nonionic surfactants are preferably aliphatic. Specific examples of nonionic surfactants include ether compounds such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, and polyoxyaralkyl alkyl ether; ester compounds such as polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxyethylene distearate ester, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquiolate, polyoxyethylene monooleate, and polyoxyethylene stearate; and acetylene glycol compounds such as 2,4,7,9-tetramethyl-5-decine-4,7-diol, 3,6-dimethyl-4-octin-3,6-diol, and 3,5-dimethyl-1-hexyn-3-ol. These may be used individually or in combination of two or more.

[0062] Cationic surfactants may be amine salts, quaternary ammonium salts, or oxyethylene-added ammonium salts. Specific examples of cationic surfactants are not limited to alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt-type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and quaternary ammonium salt-type surfactants such as benzethonium chloride. Specific examples of cationic surfactants include stearyltrimethylammonium chloride, 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. These may be used individually or in combination of two or more.

[0063] Examples of anionic surfactants include fatty acid salts (where the fatty acid has, for example, 8 to 30 carbon atoms), sulfonates (for example, alkyl sulfonic acids, alkylbenzene sulfonates (where the alkyl group has, for example, 8 to 30 carbon atoms)), and sulfate esters (for example, alkyl sulfate esters (where the alkyl group has, for example, 8 to 30 carbon atoms)). Examples of anionic surfactants include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, sodium cocoyl sarcosinate, sodium N-cocoyl methyl taurate, sodium polyoxyethylene coconut alkyl ether sulfate, sodium dietherhexyl sulfosuccinate, sodium α-olefin sulfonate, sodium lauryl phosphate, and sodium polyoxyethylene lauryl ether phosphate. These may be used alone or in combination of two or more.

[0064] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amidopropyl dimethylaminoacetic acid betaine. These may be used alone or in combination of two or more.

[0065] Nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants may each be one type or a combination of two or more. The surfactant is preferably a nonionic surfactant and / or a cationic surfactant. A combination of a nonionic surfactant and a cationic surfactant is also acceptable.

[0066] [Hardening agent] The dispersion may contain a curing agent (an active hydrogen-reactive compound or an active hydrogen-containing compound). The curing agent may also be added to the dispersion after polymerization of the non-fluorine copolymer (A).

[0067] To ensure good curing of the non-fluorinated copolymer (A), the dispersion may contain a curing agent (crosslinking agent). The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive groups present in the non-fluorinated copolymer (A). Examples of active hydrogen-reactive compounds include polyisocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds include hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0068] The curing agent may be a polyisocyanate compound. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. Polyisocyanate compounds act as crosslinking agents. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates.

[0069] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate. These include aliphatic diisocyanates such as anatomethylcaproate, lysine ester triisocyanates, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0070] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used individually or in combination of two or more.

[0071] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or mixtures thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used individually or in combination of two or more.

[0072] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate or mixtures thereof, 2,4- or 2,6-tolylenediisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used individually or in combination of two or more.

[0073] Examples of polyisocyanate derivatives include various derivatives of the polyisocyanate compounds described above, such as dimers, trimers, biuretes, allophanates, carbodiimides, uretodiones, uretoimines, isocyanurates, and iminooxadiazinediones. These may be used individually or in combination of two or more.

[0074] These polyisocyanates can be used individually or in combination of two or more types. It is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent, as the polyisocyanate compound. It is preferable to use a blocked polyisocyanate compound because it is relatively stable in aqueous solutions and can be used in the same aqueous solution as the dispersion.

[0075] Blocking agents sequester free isocyanate groups. Blocked polyisocyanate compounds can be easily reacted with hydroxyl groups by heating them to, for example, 100°C or higher, such as 130°C or higher, which regenerates the isocyanate groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. Polyisocyanate compounds can be used alone or in combination of two or more.

[0076] Epoxy compounds are compounds that contain epoxy groups. Examples of epoxy compounds include epoxy compounds containing polyoxyalkylene groups, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. A chloromethyl group-containing compound is a compound that has a chloromethyl group. Examples of chloromethyl group-containing compounds include chloromethyl polystyrene. Carboxyl group-containing compounds are compounds that have a carboxyl group. Examples of carboxyl group-containing compounds include (poly)acrylic acid and (poly)methacrylic acid.

[0077] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resin and methyl etherified melamine resin.

[0078] [Other ingredients] The dispersion may contain other components besides those listed above. Generally, other components are added after the non-fluorinated copolymer (A) is produced. Examples of other components include water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorants, fragrances, reactive silicone components, silicone resins, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components include texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, wrinkle inhibitors, shape-retaining agents, drape-retaining agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, color transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyldisodium (Chiba Specialty Chemicals Chinopearl CBS-X), dye fixatives, color fading inhibitors such as 1,4-bis(3-aminopropyl)piperazine, stain removers, and fiber As surface modifiers, enzymes such as cellulase, amylase, protease, lipase, and keratinase, as well as antifoaming agents and moisture absorption / release agents that can impart the texture and functionality of silk, include silk protein powder, their surface modifiers, and emulsified dispersions. Specifically, these can include K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Solubble S (Ichimaru Falcos), nonionic polymer compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units, such as anti-fouling agents like FR627 from Go-o Chemical Industry and SRC-1 from Clariant Japan. These may be used individually or in combination of two or more.

[0079] (Water-repellent and / or oil-repellent agents) Examples of water-repellent and / or oil-repellent agents include saturated or unsaturated hydrocarbon compounds or silicone compounds. Water-repellent and / or oil-repellent agents may be non-fluorinated. Saturated or unsaturated hydrocarbon compounds are preferably saturated hydrocarbons. The number of carbon atoms in saturated or unsaturated hydrocarbon compounds may be 15 or more, preferably 20 to 300, for example, 25 to 100. Specific examples of saturated or unsaturated hydrocarbon compounds include paraffin. Silicone compounds include, for example, silicones and siloxane-containing acrylic polymers. These may be used individually or in combination of two or more.

[0080] (Anti-slip agent) Examples of anti-slip agents include urethane resins, acrylic resins, silicones (reactive silicones, silicone resins, etc.), and combinations thereof, as well as inorganic particles such as aluminum compounds (e.g., alumina), silicon compounds (e.g., silica), and titanium compounds (which may have hydrophobic surface treatments). These may be used individually or in combination of two or more.

[0081] (Antistatic agent) Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate esters, phosphonates, and phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and its derivatives; and nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives. These may also be ion-conductive polymers obtained by polymerizing or copolymerizing monomers having cationic, anionic, or amphoteric ion-conductive groups. These may be used individually or in combination of two or more.

[0082] (Preservative) Preservatives are primarily used to enhance preservative and bactericidal properties and maintain preservation during long-term storage. Examples of preservatives include isothiazolone-type organosulfur compounds, benzisothiazolone-type organosulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol. The preservative content is preferably 0.0001 to 1% by weight relative to the total weight of the dispersion. If the preservative content is above the lower limit of the above range, the effect of adding the preservative is sufficiently obtained, and if it is below the upper limit, the storage stability of the dispersion is good.

[0083] (UV absorber) UV absorbers are chemicals that have the effect of protecting against ultraviolet rays. They absorb ultraviolet rays and convert them into infrared rays, visible light, etc., and release them. Examples of UV absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0084] (Antibacterial agent) Antibacterial agents are components that suppress the growth of bacteria on fibers and also suppress the generation of unpleasant odors derived from microbial decomposition products. Examples of antibacterial agents include cationic disinfectants such as quaternary ammonium salts (excluding component (A)), bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0085] (Deodorizer) Examples of deodorizers include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (such as the zinc complex of trisodium methylglycinediacetate described in International Publication No. 2012 / 090580).

[0086] (fragrance) While not particularly limited, lists of usable fragrance ingredients can be found in various publications, such as "Perfume and Flavor Chemicals," Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994), "Synthetic Fragrances: Chemistry and Product Knowledge," by Motoichi Indo, Chemical Daily Co. (1996), "Perfume and Flavor Materials of Natural Origin," Steffen Arctander, Allured Pub. Co. (1994), "Encyclopedia of Fragrances," edited by the Japan Fragrance Association, Asakura Shoten (1989), "Perfumery Material Performance V.3.3," Boelens Aroma Chemical Information Service (1996), and "Flower oils and Floral Compounds In Perfumery," Danute Lajaujis Anonis, Allured Pub. Co. (1993), and these are considered part of the disclosures in this specification by citation.

[0087] (Reactive silicone component) The dispersion may contain a reactive silicone component from the viewpoint of improving functionality. Examples of reactive silicone components include polysiloxanes having reactive groups in the side chain, one end, both ends, side chain and both ends, etc. However, from the viewpoint of having excellent slipperiness and antifouling properties (SR), it is preferable to use a polysiloxane having reactive groups in the side chain and / or both ends. The reactive silicone component is not particularly limited as long as it has reactive groups in the molecule, but examples include amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, methyl hydrogen silicone, etc.

[0088] Examples of amino-modified silicones include those having a structure in which an amino group is bonded to an organic group directly attached to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Alkylene groups with 2 or more carbon atoms are preferred. Divalent aromatic groups with 6 or more carbon atoms are preferred. The amino group may be a primary, secondary, or tertiary amino group. Examples of organic groups to which an amino group is bonded include: 2-aminoethyl group, N-methyl-2-aminoethyl group, N,N-dimethyl-2-aminoethyl group, N-ethyl-2-aminoethyl group, N,N-diethyl-2-aminoethyl group, N,N-methylethyl-2-aminoethyl group, 3-aminopropyl group, N-methyl-3-aminopropyl group, N,N-dimethyl-3-aminopropyl group, N-ethyl-3-anopropyl group, N,N-diethyl-3-aminopropyl group, and N,N-methylethyl-3-aminopropyl group. These functional groups may be located on the side chains or at the terminal ends of the polysiloxane.

[0089] Examples of epoxy-modified silicones include those having a structure in which an epoxy group is bonded to an organic group directly attached to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Typically, the bond with the organic group is in the form of a glycidyl ether. Examples of such functional groups include 3-glycidoxypropyl and 2-glycidoxyethyl groups. These functional groups may be located on the side chains or at the terminals of the polysiloxane.

[0090] Examples of carboxylated silicones include those having a structure in which a carboxyl group is bonded to an organic group directly connected to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Alkylene groups with two or more carbon atoms are preferred. Divalent aromatic groups with six or more carbon atoms are preferred. Examples of such functional groups include 3-carboxypropyl and 2-carboxyethyl groups. These functional groups may be located on the side chains or at the terminals of the polysiloxane.

[0091] Methylhydrogen silicone is a polydiorganosiloxane in which part of the side chain is replaced with hydrogen, and the hydrogen atoms are directly bonded to silicon atoms. When using methylhydrogen silicone, a catalyst may be used to improve reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine-based catalysts can be used. Organic acid metal salts are preferred as catalysts, and fatty acids are preferred as organic acids. From a safety standpoint, zinc stearate can be used. It is preferable to use the catalyst at a concentration of 10-40% relative to the methylhydrogen silicone, as this makes it easier to exhibit its effects. Two or more types of amino-modified, epoxy-modified, carboxy-modified, and methylhydrogen silicones may be mixed. All are silicones that have reactive groups, and it is preferable that they are silicones with film-forming properties. Film-forming properties refer to the formation of a solid film, rather than an oily or gel-like film, after the silicone is attached to the fiber surface in an emulsion state.

[0092] (Silicone resin) The dispersion may contain silicone resin from the perspective of improving functionality. The silicone resin is R3SiO 1 / 2 Unit (M units), RSiO 3 / 2 Units (T units) and SiO 4 / 2 A silicone resin consisting of at least one selected from units (Q units), where R is a linear or branched monovalent alkyl group having 1 to 18 carbon atoms, excluding silicone resins consisting only of M units or only of Q units). Silicone resin (B) is R2SiO 2 / 2 It is preferable to omit the units (D units) from the viewpoint of achieving the effects of this invention.

[0093] The silicone resin is preferably in a sol state. Examples of R include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, cetyl group, stearyl group, etc. However, considering the stability when the silicone resin (B) is in a sol state, the availability of raw materials, and cost, R is preferably a methyl group, and in particular, it is preferable that 90% or more of all R are methyl groups. Note that different types of groups may be used in combination for R.

[0094] R2SiO in silicone resin 2 / 2 The inclusion of units (D units) may impair the low-slip properties of the water repellent. Furthermore, silicone resins consisting solely of Q units may hinder the water-repellent performance of the water repellent agent.

[0095] Examples of silicone resin structures include (i) M units and Q units, (ii) M units, T units and Q units, (iii) M units and T units, (iv) T units and Q units, and (v) silicone resins consisting only of T units. Preferably, (i) silicone resins consisting of M units and Q units and (v) silicone resins consisting only of T units. The molar ratio (M / Q) of M units to Q units in (i) silicone resins consisting of M units and Q units is preferably M / Q = 0.6 to 1.3, and more preferably M / Q = 0.8 to 1.1. Two or more of these silicone resins may be used in combination.

[0096] Furthermore, silicone resin (B) may contain structural units that include hydroxyl groups bonded to silicon atoms. Specifically, (HO)RSiO 2 / 2 Units, (HO)2RSiO 1 / 2 Unit: (HO)SiO 3 / 2 Unit: (HO)2SiO 2 / 2 Unit: (HO)3SiO 1 / 2 The units may be listed, and some of the hydroxyl groups may be alkoxy groups represented by RO groups.

[0097] A sol containing silicone resin can be obtained by a manufacturing method described in Patent No. 3852921, which involves uniformly dispersing and polymerizing organodisiloxane, tetraalkoxysilane and their partially hydrolyzed condensates in water containing a surfactant, or by a manufacturing method which involves hydrolyzing the silane compounds shown below in water.

[0098] This paper details a manufacturing method for hydrolyzing silane compounds in water. Any silane compound can be used as a raw material for this manufacturing method, as long as it contains one, three, or four hydrolyzable groups, and has an alkyl group that satisfies the above conditions, and the hydrolyzable group is either chlor or alkoxy.Specifically, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrichlorosilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyl Lichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrichlorosilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, 2-ethylhexyltrichlorosilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, decyltriethoxysilane, cetyltrichlorosilane, cetyltrimethoxysilane, cetyltriethoxy Silane, stearyltrichlorosilane, stearyltrimethoxysilane, stearyltriethoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, dimethylethylchlorosilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylpropylchlorosilane, dimethylpropylmethoxysilane, dimethylpropylethoxysilane, dimethylisopropylchlorosilane, dimethylisopropylmethoxysilane, dimethylisopropylethoxysilane, dimethylisopropylethoxysilane, dimethylisopropyl methoxysilane, dimethylisopropylethoxysilane, dimethyl Methylhexylchlorsilane, dimethylhexylmethoxysilane, dimethylhexylethoxysilane, dimethyldecylchlorsilane, dimethyldecylmethoxysilane, dimethyldecylethoxysilane, dimethylcetylchlorsilane, dimethylcetylmethoxysilane, dimethylcetylethoxysilane, dimethylstearylchlorsilane, dimethylstearylmethoxysilane, dimethylstearylethoxysilane, and their partial hydrolysates are examples of usable silane compounds, but the usable silane compounds are not limited to these.Due to ease of handling, ease of removing by-products, and availability of raw materials, it is more preferable to use methoxysilane or ethoxysilane. One or more of these silane compounds may be used.

[0099] Common methods that are normally known can be used to hydrolyze silane compounds in water. These include methods in which the silane compound is added dropwise to water while the hydrolysis reaction is carried out, or methods in which water and the silane compound are mixed together and then the hydrolysis reaction is carried out. A hydrolysis catalyst may be used when carrying out the hydrolysis reaction. Conventional known catalysts can be used as hydrolysis catalysts, and it is preferable to use acidic or alkaline catalysts. In the case of acidic catalysts, solid acids such as hydrogen halides, carboxylic acids, sulfonic acids, acidic or weakly acidic inorganic salts, and ion exchange resins are preferred. In the case of alkaline catalysts, alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate, alkali metal silanolates such as sodium silanolate and potassium silanolate, amines such as triethylamine, diethylamine, and aniline, and aqueous ammonia can be used. It is preferable to adjust the amount of catalyst added so that the pH of the aqueous solution is 2 to 7 and 7 to 12. After the reaction is complete, a neutralizing agent to neutralize the acidic or alkaline catalyst may be added as needed.

[0100] A surfactant may be added to the aqueous solution to disperse the silane compound and the hydrolysis reaction product in water. There are no particular restrictions on the surfactant, but for example, anionic surfactants such as alkyl sulfates, alkylbenzene sulfons, and alkyl phosphates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene oxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene fatty acid esters; cationic surfactants such as quaternary ammonium salts and alkylamine acetates; and amphoteric surfactants such as alkyl betaines and alkylimidazolines can be used, either alone or in combination of two or more. Furthermore, surfactants that exhibit acidity or alkalinity can also be used as hydrolysis catalysts. There are no particular restrictions on the amount of surfactant to be added, but it is preferable to add 1 to 50 parts by weight per 100 parts by weight of the silane compound. If the amount is less than 1 part by weight, the effect of adding the surfactant will not be sufficiently obtained, and if it is more than 50 parts by weight, the water repellency of the water repellent may be impaired.

[0101] A mixture of water and a silane compound may be mixed with a hydrolysis catalyst and surfactant as needed, and the hydrolysis reaction may be carried out at 0-90°C for 10 minutes to 24 hours. Afterward, a neutralization reaction may be carried out as needed to obtain silicone resin. Alcohols and neutralization salts produced as by-products of the hydrolysis reaction can be removed by vacuum distillation or filtration. Various additives can be incorporated into this silicone resin. For example, preservatives and thickeners can be added depending on the purpose.

[0102] [Amount of each component] (Amount of non-fluorinated copolymer (A)) The amount of non-fluorinated copolymer (A) may be 0.01% by weight or more, 0.5% by weight or more, 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, or 30% by weight or more, relative to the dispersion. The amount of non-fluorinated copolymer (A) may be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less, relative to the dispersion. For example, during storage, it may be stored at a high concentration and, when used as a repellent (water-repellent or oil-repellent agent, water repellent, or oil repellent agent), a liquid medium may be added as needed to dilute it to any desired concentration. Due to the improved product stability, it may become possible to supply high-concentration products, which previously had supply problems due to stability issues.

[0103] (Amount of unreacted chloride monomer (a2)) The concentration of unreacted chloride monomer (a2) in the dispersion may be 10.0 ppm or less, 9.0 ppm or less, 8.0 ppm or less, 7.0 ppm or less, 6.0 ppm or less, 5.5 ppm or less, 5.0 ppm or less, 4.5 ppm or less, 4.0 ppm or less, 3.5 ppm or less, 3.0 ppm or less, 2.5 ppm or less, 2.0 ppm or less, 1.5 ppm or less, 1.0 ppm or less, 0.8 ppm or less, 0.5 ppm or less, 0.3 ppm or less, or 0.1 ppm or less.

[0104] (Amount of liquid medium (B)) The amount of liquid medium (B) may be 40% or more by weight, 50% or more by weight, 60% or more by weight, 70% or more by weight, 80% or more by weight, 90% or more by weight, 95% or more by weight, or 97% or more by weight relative to the dispersion. The amount of liquid medium (B) may be 99.9% or less by weight, 99% or less by weight, 95% or less by weight, 90% or less by weight, 80% or less by weight, 70% or less by weight, 60% or less by weight, or 50% or less by weight relative to the dispersion.

[0105] (Amount of water-soluble organic solvent (b1)) The amount of water-soluble organic solvent (b1) 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, relative to the dispersion. The amount of water-soluble organic solvent (b1) 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, relative to the dispersion.

[0106] The amount of water-soluble organic solvent (b1) may be 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 40% by weight or more, relative to the liquid medium (B). The amount of water-soluble organic solvent (b1) may be 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, 12.5% ​​by weight or less, 7.5% by weight or less, or 5.0% by weight or less, relative to the liquid medium (B).

[0107] The amount of water-soluble organic solvent (b1) may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, per 100 parts by weight of non-fluorine copolymer (A). The amount of water-soluble organic solvent (b1) may be 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per 100 parts by weight of non-fluorine copolymer (A).

[0108] The amount of water-soluble organic solvent (b1) may be 0.5 parts by weight or more, 1 part by weight or more, 1.5 parts by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, or 40 parts by weight or more, per 100 parts by weight of water. The amount of water-soluble organic solvent (b1) may be 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 25 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, per 100 parts by weight of water.

[0109] (Amount of water) The amount of water may be 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, 70% by weight or more, or 80% by weight or more, relative to the liquid medium (B). The amount of water may be 99% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, or 50% by weight or less, relative to the liquid medium (B).

[0110] (Amount of other solvents) The amount of other solvents may be 1% or more by weight, 3% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, or 40% or more by weight, relative to the liquid medium (B). The amount of other solvents may be 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, 15% or less by weight, 12.5% ​​or less by weight, 7.5% or less by weight, or 5.0% or less by weight, relative to the liquid medium (B). The dispersion does not need to contain other solvents.

[0111] (Amount of surfactant) The amount of surfactant may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, per 100 parts by weight of non-fluorine copolymer (A). The amount of surfactant may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, per 100 parts by weight of non-fluorine copolymer (A). A dispersion of non-fluorine copolymer (A) (self-emulsifying dispersion) may be formed without using a surfactant.

[0112] (Amount of hardener) The amount of curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, per 100 parts by weight of non-fluorine copolymer (A). The amount of curing agent may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, per 100 parts by weight of non-fluorine copolymer (A).

[0113] (Amount of other ingredients) The amount of other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, per 100 parts by weight of non-fluorine copolymer (A). The amount of other components may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, per 100 parts by weight of non-fluorine copolymer (A).

[0114] The amount of each component in the above-mentioned dispersion may be the same as the amount of each component in the polymerization step of the dispersion's production.

[0115] <Method for producing a dispersion> The method for producing the dispersion in this disclosure is: Step (i) of copolymerizing a hydrophobic monomer (a1) and at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride in a polymerization solvent to obtain a polymer solution containing a non-fluorine copolymer (A), and (ii) A step to reduce the concentration of unreacted chloride monomer (a2) in the obtained polymer solution to 10.0 ppm or less. Includes, The polymerization solvent contains a water-soluble organic solvent (b1), or a water-soluble organic solvent (b1) is added to the polymer solution.

[0116] [Step (i) to obtain a polymer solution containing a non-fluorinated copolymer (A)] The non-fluorinated copolymer (A) in this disclosure can be produced by any conventional polymerization method, and the conditions of the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include emulsion polymerization, solution polymerization, and suspension polymerization. It is preferable to produce the non-fluorinated copolymer (A) by emulsion polymerization or solution polymerization, and it is particularly preferable to produce it by emulsion polymerization. The polymerization solvent in the polymerization reaction contains a water-soluble organic solvent (b1), or a water-soluble organic solvent (b1) is added to the polymer solution after polymerization. It is preferable that the polymerization solvent contains a water-soluble organic solvent (b1). By including a water-soluble organic solvent (b1), it is possible to improve the emulsification and copolymerizability of the dispersion. It is also preferable to include a water-soluble organic solvent (b1) from the viewpoint of liquid-repellent performance. The amount of each component in the dispersion may be the same as the amount of each component in the polymerization solvent in the polymerization process. The amount of each component in the polymerization stage and the amount of each component in the above-mentioned dispersion may be the same.

[0117] (Emulsification polymerization) In emulsion polymerization, a method may be employed in which monomers are emulsified in a polymerization solvent in the presence of a polymerization initiator and, if necessary, a surfactant, and then polymerized by stirring at a temperature of 50 to 80°C for 30 minutes to 48 hours, for example, 3 to 24 hours, after nitrogen purging. The polymerization solvent preferably contains a water-soluble organic solvent (b1). Water-soluble polymerization initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, and ammonium persulfate, or oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate can be used. The polymerization initiator may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, per 100 parts by weight of monomer.

[0118] To obtain a dispersion with excellent stability, it is desirable to polymerize the monomers by micronizing them in water using an emulsifying device that can impart strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer. Furthermore, various anionic, cationic, or nonionic surfactants can be used as the surfactant, and they may be used in an amount ranging from 0.5 to 20 parts by weight per 100 parts by weight of the monomer. It is preferable to use anionic and / or nonionic and / or cationic surfactants.

[0119] (Solution polymerization) In solution polymerization, a method may be employed in which monomers are dissolved in a polymerization solvent in the presence of a polymerization initiator, followed by nitrogen purging, and then heating and stirring at a temperature of 30 to 120°C for 30 minutes to 48 hours, for example, 3 to 24 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The amount of polymerization initiator may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less per 100 parts by weight of monomer.

[0120] Polymerization solvents are inert to monomers and dissolve them, and may include, for example, esters (e.g., esters with 2 to 30 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 30 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols with 1 to 30 carbon atoms, specifically isopropyl alcohol), ethers, alkanes, toluene-based solvents, halogenated carbons, etc. Specific examples of polymerization solvents include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and mixed solvents thereof. The polymerization solvent may contain a water-soluble organic solvent (b1). The polymerization solvent may be 30 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more, per 100 parts by weight of the total monomers, and may be 2000 parts by weight or less, 1500 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, or 500 parts by weight or less.

[0121] (others) In polymerization, chain transfer agents may be used. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially alkyl mercaptans (e.g., with 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomer.

[0122] A solvent (water, water-soluble organic solvent (b2), etc.) may be added to the polymer solution, and a non-fluorinated copolymer (A) may also be added. For example, the monomer may be polymerized in the presence of an organic solvent to produce a non-fluorinated copolymer (A), then water may be added to the polymer mixture, and the organic solvent may be removed by distillation as needed. A surfactant may be added before or after polymerization, or it may not be added. Even if a surfactant is not added, an aqueous dispersion can be obtained by the self-emulsifying water of the polymer. A curing agent may be added before or after polymerization, but it is preferable to add it after polymerization. Other components may be added before or after polymerization.

[0123] [Chloride monomer removal process (ii)] Examples of methods for removing unreacted vinyl chloride or vinylidene chloride from the polymer solution after the polymerization reaction include distillation under reduced pressure, distillation by stirring under atmospheric pressure, distillation by bubbling air, nitrogen, or steam under heating or without heating (e.g., 100 cc / min or more, 200 cc / min or more, 300 cc / min or more, or 400 cc / min or more for 3 hours or more, 6 hours or more, 12 hours or more, or 18 hours or more), and methods using packed columns, spin coaters, cylindrical volatilizers, etc. The temperature, time, airflow strength, etc. during the removal process can be changed as appropriate. The chloride monomer (a2) may be removed while leaving at least a portion of the liquid medium in the polymer solution.

[0124] <Uses of dispersions> Examples of applications for the dispersion in this disclosure include external treatment agents (surface treatment agents) or internal treatment agents, water repellents (water repellents, oil repellents, or water- and oil-repellent agents), antifouling agents, dirt removal agents, release agents, mold release agents (external or internal mold release agents), and the like.

[0125] <Manufacturing method for processed products> The method for manufacturing the processed product in this disclosure includes the step of applying a dispersion to a substrate. [Processed Products] Substrates treated with the dispersions of this disclosure (e.g., surface treatment agents, water repellents, oil repellents, or water- and oil-repellent agents) include textile products, stone materials, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Various examples of textile products can be given. For example, natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or mixed fibers thereof. An example of a substrate treated with the dispersion will be described in detail as an example of a woven or knitted fabric.

[0126] (Woven or knitted fabrics) • Manufacturing methods for knitted fabrics Woven or knitted fabrics can be obtained by weaving or knitting the above-mentioned blended entangled yarn to obtain raw fabric, and then by post-processing and water-repellent treatment. Weaving and knitting can be carried out using known looms and knitting machines, and the preparatory processes preceding weaving and knitting can also be carried out using known equipment.

[0127] Furthermore, in post-processing, the raw fabric is first scouring and relaxed. Scouring and relaxation can be carried out in a continuous or batch manner at a temperature of 80 to 130°C. Usually, it is preferable to carry it out in a batch manner at a temperature of 100°C or lower, and it is particularly preferable to carry it out using a high-pressure liquid-jet staining machine equipped with a jet nozzle.

[0128] After scouring and relaxing, the woven or knitted fabrics are pre-set. Pre-setting is typically done using a pin tenter, dry heat treatment at 170-200°C for 30-120 seconds. After pre-setting, the fabrics are dyed according to conventional methods, followed by final setting as needed.

[0129] After post-processing, the woven or knitted fabric may be treated to be water-repellent. For water-repellent treatment, first, an aqueous solution containing a water-repellent agent (which may be a dispersion in this disclosure) is prepared. Next, the aqueous solution is applied to the woven or knitted fabric after the post-processing using a padding method, spray method, slit coater method, etc., and then dry-heat treated at 105 to 190°C for 30 to 150 seconds. The aqueous solution may also contain a crosslinking agent, softener, antistatic agent, etc., as needed. After water-repellent treatment, the woven or knitted fabric may be calendered to further improve its water-repellent performance.

[0130] Woven and knitted fabrics are suitable for clothing applications, particularly for uniforms, women's wear, and sportswear.

[0131] • Laminated fabric The present disclosure may also be provided as a laminated fabric having a breathable waterproof layer on one side of the woven or knitted fabric. The breathable waterproof layer may be directly laminated to the woven or knitted fabric, or it may be laminated to the woven or knitted fabric via an adhesive layer. When the laminated fabric of the present disclosure is used for clothing or the like, it should be positioned so that the woven or knitted fabric side is exposed to rainwater, etc.

[0132] • Breathable waterproof layer A breathable waterproof layer is a layer that covers one side of a woven or knitted fabric, and is formed from a resin that has waterproof and breathable properties.

[0133] The breathable waterproof layer may be formed by directly applying resin (the resin constituting the breathable waterproof layer) to the woven or knitted fabric, or it may be laminated to one side of the woven or knitted fabric via an adhesive layer described later. In this disclosure, a blended entangled yarn having fine protrusions due to loops or slack is used in the woven or knitted fabric. As a result, the protrusions become firmly entangled with the adhesive layer or the breathable waterproof layer, creating an anchoring effect that makes it even more difficult for the woven or knitted fabric and the breathable waterproof layer to separate. When a normal woven or knitted fabric (a woven or knitted fabric in which the above-mentioned protrusions are not sufficiently maintained on the surface) is used, the anchoring effect may not be sufficiently realized, and in such cases, the woven or knitted fabric and the breathable waterproof layer tend to separate easily.

[0134] The resin constituting the breathable waterproof layer is not particularly limited, but it is preferably composed of polyurethane resin as the main component, for example, it is preferable that polyurethane resin is contained in a proportion of 80% by mass or more. Polyurethane resin is generally suitable for forming a resin layer that has breathability and waterproofing properties. Among these, a microporous type is preferred when considering breathability, but if there is a possibility of being exposed to rain for a long time or repeated use such as washing is expected, a non-porous type of breathable polyurethane may be used instead of a microporous type.

[0135] As the polyurethane resin, conventionally known resins obtained by reacting a polyisocyanate component with a polyol component can be used.

[0136] The breathable waterproof layer may have a microporous structure or a non-porous structure. Furthermore, if it has a microporous structure, inorganic fine powder may be incorporated into the breathable waterproof layer to ensure the desired breathability.

[0137] Examples of inorganic fine powders include fine powders made from silicon dioxide, aluminum dioxide, or titanium dioxide. The average primary particle size of the inorganic fine powder is preferably about 7 to 40 nm. The inorganic fine powder content is preferably 3 to 50% by mass, and more preferably 5 to 50% by mass, relative to the total amount of the moisture-permeable waterproof layer.

[0138] The thickness of the breathable waterproof layer is preferably 5 μm or more, and more preferably 10 to 30 μm. A thickness within this range provides an excellent balance of waterproofing and breathability, and also offers advantages in terms of texture and tear strength.

[0139] ·Adhesive layer The laminated fabric preferably includes an adhesive layer. In other words, it is preferable that the woven or knitted fabric and the breathable waterproof layer are laminated via an adhesive layer. The reason for this is explained below. In this disclosure, as the woven or knitted fabric, as described above, a fabric having fine protrusions on its surface due to loops or slack is used. Therefore, the protrusions become firmly intertwined with the adhesive layer, creating an anchoring effect, which makes it even more difficult for the woven or knitted fabric and the breathable waterproof layer to separate.

[0140] Furthermore, when a breathable waterproof layer is directly laminated onto the woven or knitted fabric, for example by a coating method, protrusions on the surface of the woven or knitted fabric may penetrate the breathable waterproof layer, resulting in the formation of pinholes and inferior water resistance and strength. There is also a concern that the coating may not be uniform, leading to uneven thickness in the breathable waterproof layer. To prevent this, if the surface of the woven or knitted fabric is smoothed by calendering, for example, the protrusions or air-retaining layer may be reduced, which may decrease water repellency. Therefore, in this disclosure, it is preferable that the woven or knitted fabric and the breathable waterproof layer are laminated via an adhesive layer in order to achieve an excellent balance of water repellency, strength, and water resistance.

[0141] The type of adhesive that constitutes the adhesive layer is not particularly limited, but it is preferable that it has excellent compatibility with the breathable waterproof layer. For example, if a resin mainly composed of polyurethane resin is selected as the resin that constitutes the breathable waterproof layer, it is preferable to use an adhesive layer made of polyurethane adhesive. The polyurethane adhesive may be of any structure, such as ether-based, ester-based, or polycarbonate-based, but from the viewpoint of providing excellent breathability, ether-based adhesives are preferred.

[0142] The adhesive layer may be formed over the entire surface of one side of the woven or knitted fabric, or it may be formed in a pattern from the viewpoint of breathability or texture. The pattern is not particularly limited, but examples include dots, lines, grids, checkerboard patterns, tortoiseshell patterns, etc., and it is preferable that they are uniformly arranged throughout.

[0143] The adhesive layer thickness is preferably around 10 to 100 μm, and more preferably 20 to 80 μm. If the thickness is less than 10 μm, it is difficult to obtain a durable laminated fabric even if the adhesive occupies a large area, and if it exceeds 100 μm, the manufacturing cost increases and further adhesion cannot be expected, so neither is desirable.

[0144] • Lining fabric In the laminated fabric of this disclosure, a lining fiber fabric may be laminated on the breathable waterproof layer (on the side of the breathable waterproof layer opposite to the side on which the woven or knitted fabric of this disclosure is laminated). The lining fiber fabric can protect the breathable waterproof layer, resulting in even better waterproofing (water pressure resistance) and strength. Furthermore, by laminating the lining fiber fabric, the elongation of the entire laminated fabric can be suppressed, thereby preventing the protrusions of the blended composite yarn from being pulled and reduced due to elongation of the woven or knitted fabric caused by finishing processes after lamination or tension during wear, and thus maintaining the above-mentioned water repellency at a higher level. In addition, the water repellency can be further improved when a lining fiber fabric is laminated. The reason for this is not clear, but the inventors speculate that the water repellency is further improved because the number of lamination processes increases and the heat history the water repellent agent is subjected to increases.

[0145] Examples of lining fabrics include various woven and knitted fabrics. Among these, knitted fabrics are preferable because, compared to woven fabrics, the constituent threads tend to protrude more easily from the surface, resulting in a less flat surface, which allows for a better anchoring effect and makes it less likely to peel off from the breathable waterproof layer. In particular, tricot knitted fabric is preferable because, compared to knitted fabrics with other structures, its elasticity is suppressed, so the gaps between the stitches do not become too large, and water repellency is more effectively expressed. Furthermore, tricot knitted fabric is also preferable because it can be made into a long piece of fabric during the knitting process, resulting in fewer seams, and can be uniformly laminated on the breathable waterproof layer.

[0146] The material of the fibers constituting the lining fabric is not particularly limited and can be selected as appropriate, but nylon fibers are preferred. This is because, since acid dyes are generally used for nylon fibers, the migration and sublimation of disperse dyes to the breathable waterproof layer, which is a problem with polyester fibers and the like that use disperse dyes, is less likely to occur. The form (long fibers, short fibers, or spun yarn) or fineness of the constituent fibers of the lining fabric is not particularly limited and can be selected as appropriate within a range that does not impair the effects of this disclosure.

[0147] • Characteristics of laminated fabric The laminated fabric has excellent waterproofing properties. A preferred example of the waterproofing properties of the laminated fabric of this disclosure is a water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method), which is, for example, 10,000 mm or more, preferably 15,000 mm or more, more preferably 16,000 mm or more, and particularly preferably 20,000 mm or more. There is no particular limit to the upper limit of the water level, but examples include 50,000 mm or 25,000 mm.

[0148] Laminated fabrics have excellent moisture permeability. A preferred example of the moisture permeability of the laminated fabrics of this disclosure is a moisture permeability of, for example, 10,000 g / m² as measured according to the JIS L 1099:2012 B-1 method (potassium acetate method). 2 24 hours or more, preferably 15,000 g / m² 2 24 hours or more, more preferably 20,000 g / m² 2 • 24 hours or more is a possible example. There are no particular restrictions on the upper limit of this moisture permeability, but for example, 40,000 g / m 2 24h or 35,000g / m² 2 • 24h • mm is one example.

[0149] In the laminated fabric, delamination between the woven / knitted fabric and the breathable waterproof layer is suppressed. In the laminated fabric of this disclosure, a suitable example of the peel strength between the woven / knitted fabric and the breathable waterproof layer is, for example, 5 N / 2.54 cm or more, preferably 5 to 50 N / 2.54 cm, more preferably 6 to 30 N / 2.54 cm, and particularly preferably 9 to 25 N / 2.54 cm, as measured according to the method of JIS L 1089. To achieve the peel strength within the above range, for example, a woven / knitted fabric that has not been calendered can be used, or an adhesive layer can be provided.

[0150] • Manufacturing method of laminated fabric The method for manufacturing the laminated fabric is not particularly limited, but examples include the first and second manufacturing methods shown below. First manufacturing method: Includes the step of forming the moisture-permeable waterproof layer by applying the resin constituting the moisture-permeable waterproof layer to the surface of a woven or knitted fabric. A second manufacturing method includes the steps of forming an adhesive layer on a woven or knitted fabric or a breathable waterproof layer, and bonding the woven or knitted fabric and the breathable waterproof layer via the adhesive layer.

[0151] It is preferable to maintain as many protrusions as possible on the surface of the woven or knitted fabric used in the laminated fabric (i.e., the woven or knitted fabric of the present disclosure described above). For example, if calendering is applied to the woven or knitted fabric to facilitate coating or other processes, the fine protrusions of the blended entangled yarns may be flattened, resulting in a flat surface, and it may not be possible to achieve a specific water droplet rolling angle. Furthermore, if calendering is applied, it may not be possible to sufficiently maintain the above-mentioned air-retaining layer, and the desired water repellency may not be achieved. Therefore, it is preferable to carefully consider the conditions for calendering. For example, when calendering a woven or knitted fabric, it is advisable to use normal conditions (e.g., a temperature of 130°C or higher and a linear pressure of 200 to 20000 N / cm) that do not reduce the protrusions of the blended entangled yarns too much. Note that calendering may also be performed without heating.

[0152] In the first manufacturing method, a coating method can be used to apply the resin constituting the moisture-permeable waterproof layer to the surface of the woven or knitted fabric. In the coating method, a knife coater or a comma coater can be used. Furthermore, from the viewpoint of providing excellent moisture permeability, it is preferable to obtain the moisture-permeable waterproof layer by a wet method.

[0153] In the second manufacturing method, a lamination method is used as a method for forming an adhesive layer on a woven or knitted fabric or a breathable waterproof layer. In the lamination method, a resin solution or a hot melt method can be used to form the adhesive layer. First, a resin composition for forming a breathable waterproof layer (for example, a resin composition containing a resin and an organic solvent) is applied to the surface of a release agent (release paper, release cloth, or release film, etc.) with a clearance, and the breathable waterproof layer is formed while adjusting the thickness. The mixture is then heat-treated to allow it to react completely and obtain a film. The release agent can be removed as appropriate after lamination or curing.

[0154] Then, an adhesive layer is formed on the woven or knitted fabric or the breathable waterproof layer. For example, if a resin solution is used, a two-component curing polyurethane resin solution, adjusted to a viscosity in the range of 500 to 5000 mPa·s, may be applied to the entire surface or in a pattern. After drying, an adhesive layer is formed, and the woven or knitted fabric and the breathable waterproof layer are bonded together via the adhesive layer, and the second manufacturing method can be carried out by pressing or heat-pressing the two together.

[0155] On the other hand, in the case of hot melt, it is preferable to use a moisture-curing resin that reacts with moisture in the air, and in practical terms, it is more preferable to use one that melts in a temperature range of about 80 to 150°C. In this case, first, the hot melt resin is melted while considering the melting point of the resin and the viscosity when melted. Then, the molten resin is applied onto the woven or knitted fabric or the moisture-permeable waterproof layer and allowed to mature while cooling at room temperature to form an adhesive layer. After that, the woven or knitted fabric and the moisture-permeable waterproof layer are bonded together via the adhesive layer and pressed together to carry out the second manufacturing method.

[0156] In the manufacturing method, it is preferable to adopt the second manufacturing method. This is because, when a moisture-permeable waterproof layer is laminated using a coating method, there is a concern that pinholes may occur in the moisture-permeable waterproof layer due to fine protrusions on the surface of the woven or knitted fabric, which tends to reduce water pressure resistance. Furthermore, if calendering is applied to the woven or knitted fabric in an attempt to form a uniform moisture-permeable waterproof layer, there is a concern that the protrusions or air-retaining layer will be reduced, making it impossible to achieve the desired water repellency. This necessitates a separate examination of the calendering conditions, which can complicate the process itself.

[0157] Subsequently, a lining fabric can be laminated onto the breathable waterproof layer using a known and appropriate method.

[0158] • Uses of laminated fabrics Laminated fabrics offer excellent water repellency and breathable waterproofing, and the breathable waterproof layer does not peel off even in harsh environments, making them suitable for use in fields such as uniforms, sportswear, and outdoor products used outdoors.

[0159] [Processing method] The dispersion of this disclosure can be applied to a substrate by conventionally known methods as a treatment agent (particularly a surface treatment agent). The dispersion of this disclosure may be diluted by dispersing it in an organic solvent or water as needed, and then applied to the surface of the substrate by known methods such as immersion coating, spray coating, or foam coating, followed by drying. If necessary, it may also be applied together with a suitable crosslinking agent and cured. Furthermore, the dispersion of this disclosure can be used in combination with various additives such as water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insecticides, defoamers, etc. Examples of various additives may be the same as those described in "other components" of the dispersion above. The concentration of the non-fluorine copolymer in the treatment agent that comes into contact with the substrate may be appropriately changed depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0160] [Textile products] Various examples of textile products can be given as the base material, but cloth products and paper products are examples.

[0161] Examples of textile products include natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or blends thereof. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as fabrics and carpets. However, treatment may also be applied to fibers, yarns, and intermediate fiber products (e.g., slivers or rovings) before they are made into fabric.

[0162] Examples of paper products include paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as crushed wood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine, recycled corrugated cardboard or deinked paper, paper containers, and molded products made from paper. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-grade paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc.

[0163] The dispersion can be applied to the textile product (e.g., cloth) by any known method for treating the textile product with a liquid. The textile product may be immersed in the dispersion, or the solution may be applied to or sprayed onto the textile product. The treated textile product is preferably dried and cured by heating to exhibit water-repellent and oil-repellent properties. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. Good performance can also be obtained with low-temperature heating (e.g., 100°C to 140°C) in this disclosure. The heating time may be 5 seconds to 60 minutes in this disclosure, for example, 30 seconds to 3 minutes.

[0164] Alternatively, the polymer may be applied to textile products by cleaning methods, for example, by washing or dry cleaning.

[0165] The textile products to be processed may be cloths, including woven fabrics, knitted fabrics and nonwoven fabrics, cloths in the form of clothing and carpets, but may also be fibers or yarns or intermediate textile products (e.g., slivers or rovings). The dispersions of the present disclosure are particularly effective in making textile products (e.g., synthetic fibers) water-repellent and / or oil-repellent.

[0166] The fibers that make up the textile product may be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, or inorganic fibers. The fibers may be used individually or in combination of two or more types.

[0167] Examples of natural fibers include cellulose fibers such as cotton, flax, and pulp, as well as chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as groundwood pulp (GP), pressured groundwood pulp (PGW), and thermomechanical pulp (TMP); chemical pulps such as high-yield unbleached softwood kraft pulp (HNKP; N material), bleached softwood kraft pulp (NBKP; N material, NB material), unbleached hardwood kraft pulp (LUKP; L material), and bleached hardwood kraft pulp (LBKP, L material); and recycled paper pulps such as deinking pulp (DIP) and waste pulp (WP), as well as semi-chemical pulps (CP).

[0168] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymerized polyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; and polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupro, polynosic rayon, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0169] Alternatively, the textile product may be leather. The manufacturing polymer may be applied to the leather in the form of an aqueous solution or aqueous emulsion at various stages of leather processing, for example, during the wetting process or during the finishing process, in order to make the leather hydrophobic and oleophobic. Alternatively, the textile product may be paper. The manufacturing polymer may be applied to pre-formed paper, or it may be applied at various stages of papermaking, for example, during the drying period of the paper.

[0170] "Processing" refers to applying the dispersion to a substrate by means of immersion, spraying, coating, etc. Through processing, the polymer, which is the active ingredient of the dispersion, penetrates into the interior of the substrate and / or adheres to the surface of the substrate.

[0171] [Pretreatment of textile products] Textile products may be pre-treated before being treated with the dispersion of this disclosure. Pre-treating the textile products can impart excellent fastness to the textile products after treatment with the dispersion.

[0172] Examples of pretreatments for textile products include cationization by reaction with reactive quaternary ammonium salts, anionization by sulfonation, carboxylation, phosphorylation, etc., acetylation, benzoylation, carboxymethylation, grafting, tannic acid treatment, and polymer coating after anionization.

[0173] The method for pre-treating textile products is not limited, but conventionally known methods can be used. This may involve dispersing and diluting the pre-treatment solution in an organic solvent or water as needed, applying it to the surface of the textile product by known methods such as immersion coating, spray coating, or foam coating, and then drying it. The pH and temperature of the pre-treatment solution may be adjusted according to the desired degree of treatment. As an example of a method for pre-treating textile products, a method for pre-treating textile products with a non-fluorine water-repellent agent will be described in detail.

[0174] (Pretreatment of textile products with non-fluorine water repellent) The method for manufacturing pre-treated textile products is -SO3M 1 (In the formula, M 1 (represents a monovalent cation) a monovalent group represented by -COOM 2 (In the formula, M 2 A monovalent group represented by (where is a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2A step of applying at least one non-fluorine-based water repellent selected from the group consisting of an acrylic water repellent, a silicone water repellent, and a dendrimer water repellent may be provided to a fiber containing at least one functional group (hereinafter sometimes referred to as a "specific functional group") selected from the group consisting of monovalent groups represented by (each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

[0175] 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 it is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0176] The fiber containing the specific functional group (hereinafter sometimes referred to as a "functional group-containing fiber") can be prepared, for example, by the following method. (i) A compound having the specific functional group is adhered to the fiber material. The adhesion 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 specific functional group remains. (ii) A fiber in which the specific functional group is directly introduced into the material constituting the fiber is prepared.

[0177] In the case of (i), for example, a functional group-containing fiber can be obtained by a functional group introduction step of treating the fiber material with a pretreatment liquid containing one or more compounds having the specific functional group.

[0178] There are no particular restrictions on the material of the fiber material, and examples include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene; and composite fibers and blended fibers thereof. The fiber material may take any form, such as fibers (tow, sliver, etc.), yarn, knitted fabrics (including interwoven fabrics), woven fabrics (including interwoven fabrics), nonwoven fabrics, and paper.

[0179] In this embodiment, from the viewpoint of obtaining good water repellency in the resulting textile product, polyamide is used. It is preferable to use fiber materials that include polyester as a material, and in particular, it is preferable to use nylon such as nylon 6, nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.

[0180] The above -SO3M 1 As a compound having this property, phenolic polymers can be used. Examples of such phenolic polymers include those containing at least one compound represented by the following general formula.

[0181] TIFF2023178300000004.tif5382[where, X 2 -SO3M 3 (In the formula, M 3 (where n represents a monovalent cation) or a group represented by the following general formula, where n is an integer between 20 and 3000.

[0182] TIFF2023178300000005.tif3968[In formula, M 4 This represents a monovalent cation.

[0183] The above M 3 Examples include H, K, Na, or ammonium ions which may have substituents.

[0184] The above M 4Examples include H, K, Na, or ammonium ions which may have substituents.

[0185] 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.

[0186] The above-COOM 2 Examples of compounds having this property include polycarboxylic acid polymers.

[0187] Examples of polycarboxylic acid polymers include acrylic acid, methacrylic acid, and maleic acid. Polymers synthesized by conventionally known radical polymerization methods using monomers such as these, or commercially available polymers, can be used.

[0188] One method for producing polycarboxylic acid polymers is to add a radical polymerization initiator to an aqueous solution of the monomer and / or its salt, and heat the reaction at 30 to 150°C for 2 to 5 hours. At this time, alcohols such as methanol, ethanol, and isopropyl alcohol, or aqueous solvents such as acetone may be added to the aqueous solution of the monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators such as combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo polymerization initiators. These radical polymerization initiators may be used alone or in combination of two or more. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.

[0189] In radical polymerization, copolymerizable monomers other than those mentioned above can be used. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, as well as acrylamide, acrylates, and methacrylates. Acrylates and methacrylates are preferably those having a hydrocarbon group with 1 to 3 carbon atoms, which may have substituents such as hydroxyl groups. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used individually or in combination of two or more.

[0190] The carboxyl groups in polycarboxylic acid polymers may be free or neutralized by alkali metals or amine compounds. Examples of alkali metals include sodium, potassium, and lithium, while examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0191] The weight-average molecular weight of the polycarboxylic acid polymer is preferably 1,000 to 20,000, and more preferably 3,000 to 15,000, from the viewpoint of obtaining good water repellency in the resulting textile product.

[0192] For polycarboxylic acid polymers, commercially available products such as "NeoCrystal 770" (manufactured by Nikka Chemical Co., Ltd., product name) and "Cellopol PC-300" (manufactured by Sanyo Chemical Industries, Ltd., product name) can be used.

[0193] The above - OP(O)(OX 1 )(OX 2 Examples of compounds having the following general formula include phosphate ester compounds. [ka] [In the formula, X1 or X 2 is synonymous with the above, X 3 represents an alkyl group having 1 to 22 carbon atoms.]

[0194] As the above phosphate ester compound, a monoester, diester, and triester of phosphoric acid in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and a mixture thereof can be used.

[0195] From the viewpoint of obtaining a fiber product with good water repellency, it is preferable to use lauryl phosphate ester and decyl phosphate ester.

[0196] As the phosphate ester compound, commercially available products such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name) can be used.

[0197] The pretreatment liquid containing one or more of the above compounds having a specific functional group can be, for example, an aqueous solution of the above-mentioned compounds. Further, the pretreatment liquid may contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0198] Methods for treating fibrous materials with the above-mentioned pretreatment solution include, for example, padding, immersion, spraying, and coating. For padding, for example, methods using padding equipment described on pages 396-397 of the Dictionary of Textile Dyeing and Processing (published in 1963 by Nikkan Kogyo Shimbun) and pages 256-260 of Color Dyeing Chemistry III (published in 1975 by Jikkyo Shuppan Co., Ltd.) can be used. For coating, for example, methods using coating machines described on pages 473-477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used. For immersion, for example, methods using batch-type dyeing machines described on pages 196-247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used, and liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, cheese dyeing machines, etc. can be used. Examples of spray treatments include air sprays that atomize the treatment solution using compressed air, and air sprays that use a hydraulic atomization system. The concentration of the treatment solution and the treatment conditions such as heat treatment after application can be adjusted as appropriate, taking into account the purpose, performance, and other conditions. If the pretreatment solution contains water, it is preferable to dry it to remove the water after it has been applied to the fiber material. There are no particular restrictions on the drying method, and either a dry heat method or a wet heat method may be used. There are no particular restrictions on the drying temperature, but for example, drying at room temperature to 200°C for 10 seconds to several days is sufficient. If necessary, after drying, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes.

[0199] Furthermore, if the fiber material is to be dyed, the pretreatment with the pretreatment solution may be performed before dyeing or in the same bath as the dyeing. However, if reducing soaping is performed, there is a risk that the compounds having the above-mentioned specific functional groups (for example, phenolic polymer compounds, etc.) that have been adsorbed during the process may be removed. Therefore, it is preferable to perform the pretreatment after reducing soaping following dyeing.

[0200] The treatment temperature during the immersion process can be 60 to 130°C. The treatment time can be 5 to 60 minutes.

[0201] In the functional group introduction step using the pretreatment solution, it is preferable to treat the material in such an amount that the amount of compound having the specified functional group attached is 1.0 to 7.0 parts by mass per 100 parts by mass of the fiber material. Within this range, a high level of both durable water repellency and texture can be achieved.

[0202] The pretreatment solution is preferably adjusted to a pH of 3-5. pH adjustment can be done using pH adjusting agents such as acetic acid or malic acid.

[0203] The pretreatment solution may also contain salt to effectively adsorb the compound having the above-mentioned specific functional group onto the fiber material through a salting-out effect. Examples of salts that can be used include sodium chloride. Examples include sodium carbonate, ammonium sulfate, and sodium sulfate.

[0204] In the functional group introduction step using a pretreatment solution, it is preferable to remove any compounds having the specified functional groups that have been excessively treated. One method of removal is washing with water. By ensuring sufficient removal, it is possible to suppress the inhibition of water repellency development in the subsequent water-repellent treatment, and in addition, the texture of the resulting textile product will be improved. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fibers before contacting them with a non-fluorine-based water repellent.

[0205] (ii) Examples of fibers in which the above-mentioned specific functional groups are directly introduced into the material constituting the fiber include cationic dyeable polyester (CD-PET).

[0206] From the viewpoint of obtaining good water repellency in the resulting textile product, the functional group-containing fibers preferably have a surface zeta potential of -100 to -0.1 mV, and more preferably -50 to -1 mV. The surface zeta potential of the fibers can be measured, for example, using the zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.). [Examples]

[0207] Examples of the embodiments described herein will be explained in detail below, but these examples are not intended to limit the disclosure. In the following, % refers to weight % unless otherwise specified.

[0208] The meanings of the abbreviations are as shown in Table 1.

[0209] [Polymerization Example 1] In a 500ml plastic container, add stearyl acrylate (CH2=CHC(=O)OC 18 H 37 80g of ), 3g of cationic emulsifier, 6g of sorbitan fatty acid ester, 25g of tripropylene glycol as a water-soluble glycol solvent, and 200g of pure water were charged together. The mixture was heated to 60°C, stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed using ultrasound for 15 minutes. The emulsion dispersion was transferred to a 500ml autoclave, purged with nitrogen for 15 minutes, and then 0.2g of lauryl mercaptan and 20g of vinyl chloride were charged. Further, 1g of azo group-containing water-soluble initiator was added, and the mixture was heated to 60°C and reacted for 4 hours to obtain an aqueous dispersion of the polymer. The monomer conversion rate by gas chromatography was 99.0-99.8%. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a solid content of approximately 30% by weight. Next, the mixture was heated to 60°C and stirred while bubbling with nitrogen gas at a rate of 500 cc / min for 24 hours to remove unreacted vinyl chloride monomers and obtain an aqueous dispersion containing the non-fluorine copolymer (A). Gas chromatography analysis revealed no remaining vinyl chloride monomers (detection limit: 1 ppm).

[0210] [Polymerization Examples 2-8 and Comparative Polymerization Example 1] An aqueous dispersion containing a non-fluorine copolymer (A) was obtained in the same manner as in polymerization example 1, except that the amounts of monomer and liquid medium used were changed as shown in Table 1.

[0211] [Example 1] A vinyl chloride monomer was added to the aqueous dispersion obtained in polymerization example 1 to a concentration of 2 ppm to obtain an aqueous dispersion containing a non-fluorinated copolymer (A) with a vinyl chloride concentration of 2 ppm. The vinyl chloride concentration was confirmed by gas chromatographic analysis. The obtained aqueous dispersion was diluted with tap water to prepare 1000 g of a test solution with a solid content of 1.0%. A polyester fabric was immersed in this test solution, then squeezed with a mangle, and the fabric was passed through a pin tenter at 160°C for 1 minute, dried, and cured. Using the fabric treated in this manner, water repellency tests, Bundesmann tests, abrasion fastness tests, and chalk mark tests were performed as described below. The results are shown in Table 2.

[0212] [Examples 2-9, Comparative Examples 1-3] An aqueous dispersion was obtained in the same manner as in Example 1, except that the aqueous dispersion obtained in the polymerization example shown in Table 2 was used and the vinyl chloride concentration was changed as shown in Table 2. The following tests were performed on the obtained aqueous dispersion. The results are shown in Table 2.

[0213] [Water repellency test] After storing the treated test fabrics in a constant temperature and humidity chamber at 21°C and 65% humidity for at least 4 hours, the following evaluations were performed. The water repellency of each test fabric was evaluated according to the spray method of JIS-L-1092 (AATCC-22). Water repellency was evaluated according to the criteria shown below. A higher score indicates better water repellency. The results are shown in Table 2.

[0214] TIFF2023178300000007.tif32151

[0215] [Bundesmann Exam] For each of the test fabrics described above, rainfall was induced according to the Bundesmann test described in JIS-L-1092(C) under the conditions of a rainfall rate of 80 cc / min, a rainwater temperature of 20°C, and a rainfall duration of 1 minute, and the amount of water leakage (mL) was measured. The amount of water leakage refers to the amount of water (ml) that passed through the surface of the fabric during the Bundesmann test. The results are shown in Table 2.

[0216] [Friction fastness test] For each of the test cloths described above, a test piece measuring 220 mm in length and 30 mm in width was prepared according to the friction tester type II (Gakushin type) method described in JIS-L-0849. The test piece was attached securely using double-sided tape, and a friction element with a white cotton cloth attached was placed on top. A load of 2N was applied, and friction was performed 100 times. After the test, the white cotton cloth covering the friction element was removed, and the result was determined using a gray scale for staining. The results are shown in Table 2.

[0217] [Product stability test (sedimentation)] A dispersion solution adjusted to a solid content of 30% by weight was left at 50°C for two weeks. The state of the dispersion was then visually observed and evaluated according to the following criteria. The results are shown in Table 2. ◎: No change in appearance ○: No sedimentation is observed, but a very small amount of precipitate is visible on the surface of the dispersion. △: Slight sedimentation is observed, and a very small amount of precipitate is seen on the surface of the dispersion. ×: Separation or sedimentation is observed.

[0218] [Chalk Mark Test] Each of the test cloths described above was placed on a flat surface, and the surface of the test cloth was lightly scratched with a fingernail. The traces left behind, resembling chalk, were visually evaluated. The results are shown in Table 2. ◎: No trace at all ○: The trail appears faint. △: The trajectory is visible ×: The trail appears darker. [Table 1] [Table 2]

[0219] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Industrial applicability]

[0220] The dispersions of this disclosure can be used to impart water repellency to various products.

Claims

1. A repeating unit derived from a hydrophobic monomer (a1), a repeating unit derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride; a repeating unit derived from a cyclic hydrocarbon group-containing monomer (a3), which is an optional component; a repeating unit derived from the crosslinkable monomer (a4), which is an optional component; and a fluorine-free copolymer (A) comprising a repeating unit derived from a monomer (a5) other than the monomers (a1) to (a4), which is an optional component; and a liquid medium (B) containing a water-soluble organic solvent (b1) having at least two groups selected from the group consisting of a hydroxy group and an ether group; the concentration of unreacted chloride monomer (a2) is 3 ppm or less; the amount of repeating units derived from the hydrophobic monomer (a1) in the copolymer (A) is 35% by weight or more; the amount of repeating units derived from the chloride monomer (a2) is 3% by weight or more in the copolymer (A); the amount of repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​in the copolymer (A) is 15% by weight or less, the amount of repeating units derived from the crosslinkable monomer (a4) in the copolymer (A) is 15% by weight or less, the amount of repeating units derived from the other monomer (a5) in the copolymer (A) is 15% by weight or less, 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 an aliphatic hydrocarbon group having 10 to 30 carbon atoms; R 12 is a hydrogen atom, a methyl group, or a chlorine atom; Y 11 is -O-, -O-(CH 2 ) m -O-C(═O)-NH-, -O-(CH 2 ) m -NH-C(═O)-O-, or -O-(CH 2 ) m -NH-C(═O)-, -O-(CH 2 ) m -NH-C(═O)-NH-, -O-(CH 2 ) m -NH-S(═O) 2 - or -O-(CH 2 ) m -S(═O) 2 -NH- [wherein m is an integer of 1 to 5], k is 1. is a compound represented by The water-soluble organic solvent (b1) has a boiling point of 140°C or higher and 350°C or lower.

2. A dispersion liquid as described in claim 1, wherein the hydrocarbon group in the hydrophobic monomer (a1) is a linear alkyl group having 10 or more carbon atoms.

3. A dispersion liquid described in claim 1 or 2, wherein the hydrophobic monomer (a1) has an amide group, a urea group or a urethane group.

4. A dispersion liquid described in any one of claims 1 to 3, wherein the copolymer (A) contains a repeating unit derived from the cyclic hydrocarbon group-containing monomer (a3).

5. A dispersion described in any one of claims 1 to 4, wherein the copolymer (A) contains a repeating unit derived from the crosslinkable monomer (a4).

6. A dispersion described in any one of claims 1 to 5, wherein the amount of repeating units derived from the hydrophobic monomer (a1) in the copolymer (A) is 45% by weight or more.

7. A dispersion described in any one of claims 1 to 6, which is an aqueous dispersion.

8. The dispersion liquid according to claim 1, wherein the water-soluble organic solvent (b1) is a glycol compound or a monoalkyl ether thereof.

9. The dispersion liquid according to claim 1, wherein the amount of the water-soluble organic solvent (b1) is 5 parts by weight or more and 80 parts by weight or less per 100 parts by weight of the copolymer (A).

10. A process (i) of copolymerizing a hydrophobic monomer (a1) and at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride in a polymerization solvent to obtain a polymer solution containing a non-fluorinated copolymer (A); and a step (ii) of reducing the concentration of the unreacted chloride monomer (a2) in the obtained polymer solution to 3 ppm or less; Including, the polymerization solvent contains a water-soluble organic solvent (b1), or the water-soluble organic solvent (b1) is added to the polymer solution, the water-soluble organic solvent (b1) has at least two groups selected from the group consisting of a hydroxy group and an ether group, The fluorine-free copolymer (A) is A repeating unit derived from the hydrophobic monomer (a1), A repeating unit derived from the chloride monomer (a2), a repeating unit derived from a cyclic hydrocarbon group-containing monomer (a3), which is an optional component; a repeating unit derived from the crosslinkable monomer (a4), which is an optional component; and and a repeating unit derived from an optional monomer (a5) other than the monomers (a1) to (a4). the amount of repeating units derived from the hydrophobic monomer (a1) in the copolymer (A) is 35% by weight or more; the amount of repeating units derived from the chloride monomer (a2) in the copolymer (A) is 3% by weight or more; the amount of repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​in the copolymer (A) is 15% by weight or less, the amount of repeating units derived from the crosslinkable monomer (a4) in the copolymer (A) is 15% by weight or less, the amount of repeating units derived from the other monomer (a5) in the copolymer (A) is 15% by weight or less, 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 an aliphatic hydrocarbon group having 10 to 30 carbon atoms; R 12 is a hydrogen atom, a methyl group, or a chlorine atom; Y 11 is —O—, —O—(CH 2 ) m —O—C(═O)—NH—, —O—(CH 2 ) m —NH—C(═O)—O—, —O—(CH 2 ) m —NH—C(═O)—, —O—(CH 2 ) m —NH—S(═O) 2 —, or —O—(CH 2 ) m —S(═O) 2 —NH— [wherein m is an integer of 1 to 5], k is 1. is a compound represented by The method for producing a dispersion, wherein the boiling point of the water-soluble organic solvent (b1) is 140°C or higher and 350°C or lower.

11. A water repellent agent which is a dispersion liquid described in any one of claims 1 to 9.

12. A method for producing a treated product, comprising the step of applying a dispersion according to any one of claims 1 to 9 to a substrate.

13. A textile product treated with the dispersion liquid described in any one of claims 1 to 9.