Dispersion

Abstract

To provide: a dispersion with which it is possible to achieve excellent processing stability of an organo-modified silicone and excellent water wicking resistance (anti-wicking property) and hue of a fiber product; a fiber product treated with the dispersion liquid; and a method for producing the fiber product. In one embodiment, provided is a dispersion containing an organo-modified silicone (alpha) having a specific structure, wherein the amount of cyclic siloxane (gamma) having a specific structure in the dispersion is 1000 mass ppm or less. In one embodiment, the dispersion further includes a hydrophobic polymer (beta) having a specific structure.

Description

dispersion liquid

[0001] The present invention relates to a dispersion and to textile products treated with said dispersion.

[0002] Conventionally, water-repellent aids and water-repellent compositions containing an organo-modified silicone and a hydrophobic polymer have been known for imparting water repellency to textile products and the like. Patent Document 1 describes a water-repellent aid for non-fluorine-based water repellents, which contains an organo-modified silicone of a specific structure. Patent Document 2 describes a surface treatment agent comprising (A) a water- and oil-repellent polymer having repeating units derived from at least one water- and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine-containing monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms, in an amount of 30 to 100% by weight based on the water- and oil-repellent polymer; (B) a silicone polymer of a specific structure; and (C) a liquid medium.

[0003] International Publication No. WO 2017 / 150176 International Publication No. WO 2019 / 163570

[0004] The technology described in Patent Document 1 aims to obtain a water-repellent auxiliary that can improve the durable water repellency of non-fluorinated water repellents, while the technology described in Patent Document 2 aims to obtain a surface treatment agent that is excellent in water and oil repellency and slip resistance. However, these technologies did not provide sufficient processing stability for the organo-modified silicone in the treatment agent, or sufficient water wicking resistance (anti-wicking properties) and color of the textile product treated with the treatment agent.

[0005] The present invention has an object to solve the above-mentioned problems and to provide a dispersion that can achieve excellent processing stability of organo-modified silicones and good water wicking resistance (anti-wicking properties) and color of textile products, a textile product treated with the dispersion, and a method for producing the textile product.

[0006] The present disclosure includes the following items: [Item 1] A compound represented by the following general formula (1): [In formula (1), R 20 , R 21 and R 22 each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms; R 23represents a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 carbon atoms; R 30 , R 31 , R 32 , R 33 , R 34 and R 35 each independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 carbon atoms; a represents an integer of 0 or more, b represents an integer of 1 or more, (a+b) is 10 to 200, and when a is 2 or more, a plurality of R 20 and R 21 may be the same or different, and when b is 2 or more, a plurality of R 22 and R 23 may be the same or different.] In the dispersion, an organo-modified silicone (α) represented by the following general formula (1a): [In formula (1a), R 20 and R 21 each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and a1 is an integer of 30 or less.] A dispersion in which the amount of cyclic siloxane (γ) represented by the formula (1) is 1000 mass ppm or less. [Item 2] A dispersion in which the amount of cyclic siloxane (γ) represented by the formula (1) is 1000 mass ppm or less. 23 is a saturated hydrocarbon group having 6 to 50 carbon atoms. [Item 3] The dispersion according to Item 1 or 2, further comprising a hydrophobic polymer (β), wherein the hydrophobic polymer is one or more selected from the group consisting of urethane polymers and acrylic polymers. [Item 4] The acrylic polymer is a compound represented by the following general formula (A-1): [In formula (A-1), R 1 represents a hydrogen atom or a methyl group, and R 2represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent.] [Item 5] The dispersion according to Item 3 or 4, wherein the acrylic polymer further contains a structural unit derived from a monomer (VC) which is one or more monomers selected from the group consisting of vinyl chloride and vinylidene chloride. [Item 6] The dispersion according to Item 3 or 4, wherein the acrylic polymer further contains a structural unit derived from a monomer (VC) which is one or more monomers selected from the group consisting of vinyl chloride and vinylidene chloride. [Item 7] The dispersion according to Item 3 or 4, wherein the acrylic polymer further contains a structural unit derived from a monomer (VC) which is one or more monomers selected from the group consisting of vinyl chloride and vinylidene chloride. [In formula (A-2), R 11 represents a hydrogen atom or a methyl group; R 12 represents a divalent hydrocarbon group having 1 to 6 carbon atoms; Z represents an ester group or an amide group; W is —CO—R 13 (In the formula, R 13 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, a —NH—CO—NH group, or a group represented by the following formula (A-3): [Item 7] The dispersion according to any one of items 3 to 5, further comprising a structural unit derived from a monomer (A-2) represented by the following general formula (I-1): [Item 7] The acrylic polymer (B1) has an HLB of 7 to 18 and is represented by the following general formula (I-1): [In formula (I-1), R 3 represents a hydrogen atom or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, Y 1 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.], (B2) a compound having an HLB of 7 to 18 and represented by the following general formula (II-1): [In formula (II-1), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group; Y 2 and (B3) a compound having an HLB of 7 to 18, in which an alkylene oxide having 2 to 4 carbon atoms is added to an oil or fat having a hydroxyl group and a polymerizable unsaturated group. [Item 8] The dispersion according to any one of Items 3 to 6, wherein the urethane polymer further contains a structural unit derived from at least one reactive activator (B) selected from the group consisting of a compound represented by the following general formula (UI-1): R U31 [-W1 -R U32 ] d [-V 1 ] e (UI-1) [In formula (UI-1), d represents an integer of 1 or more, e represents an integer of 2 or more, (d+e) is 3 to 6, and R U31 represents a (d+e) valent organic group, W 1 represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group; R U32 represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms; V 1 represents a hydroxy group, an amino group, or a carboxy group, provided that e V 1 and a structural unit derived from a polyfunctional compound represented by the following general formula (UII): R U33 [-NCO] f (UII) [In formula (UII), R U33 represents an f-valent organic group, and f represents an integer of 2 to 7.] and a hydrophobic compound having a structural unit derived from an isocyanate compound represented by the formula: [Item 9] A method for producing the dispersion according to any one of Items 3 to 8, comprising a mixing step of mixing an emulsion containing the organo-modified silicone (α) with the hydrophobic polymer (β). [Item 10] A method for producing the dispersion according to any one of Items 3 to 8, comprising a polymerization step of polymerizing monomer components that are raw materials for the hydrophobic polymer (β) in the presence of the organo-modified silicone (α) to obtain a dispersion. [Item 11] The method according to Item 10, wherein the polymerization step is carried out in the presence of an emulsion containing the organo-modified silicone (α). [Item 12] A textile product treated with the dispersion according to any one of Items 1 to 8. [Item 13] A method for producing a textile product, comprising a step of treating a substrate with the dispersion according to any one of Items 1 to 8.

[0007] According to one aspect of the present invention, it is possible to provide a dispersion that can achieve excellent processing stability of organo-modified silicone, and good water wicking resistance (anti-wicking properties) and color of textile products, a textile product treated with the dispersion, and a method for producing the textile product.

[0008] A preferred embodiment of the present invention (hereinafter also referred to as the present embodiment) will be described in detail below, although the present invention is not limited to the following embodiment.

[0009] <<Dispersion>> One aspect of the present invention is a dispersion liquid comprising a compound represented by the following general formula (1): [In formula (1), R 20 , R 21 and R 22 each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms; R 23 represents a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 carbon atoms; R 30 , R 31 , R 32 , R 33 , R 34 and R 35 each independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 carbon atoms; a represents an integer of 0 or more, b represents an integer of 1 or more, (a+b) is 10 to 200, and when a is 2 or more, a plurality of R 20 and R 21 may be the same or different, and when b is 2 or more, a plurality of R 22 and R 23 may be the same or different.] In the dispersion, an organo-modified silicone (α) represented by the following general formula (1a): [In formula (1a), R 20 and R 21 each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and a1 is an integer of 30 or less.] The present invention provides a dispersion in which the amount of cyclic siloxane (γ) represented by the following formula is 1,000 ppm by mass or less.

[0010] <Cyclic siloxane (γ)> The cyclic siloxane (γ) present in the dispersion is typically a by-product produced during the synthesis of hydrogen silicone, which is the raw material for organo-modified silicone (α). Due to the structure represented by general formula (1a), cyclic siloxane (γ) tends to have a lower melting point and lower water repellency than organo-modified silicone (α). The present inventors have found through their studies that the presence of a large amount of such cyclic siloxane (γ) in a dispersion containing organo-modified silicone (α) can result in (1) deterioration of processing stability, typified by the adhesion of a gum-like substance (gum-up) to equipment used in treating a substrate with the dispersion (for example, a mangle used in squeezing a substrate treated with the dispersion to produce a textile product), (2) insufficient water wicking resistance (anti-wicking property) of the textile product treated with the dispersion, and / or (3) poor color of the textile product treated with the dispersion. Therefore, it is considered advantageous to have a small amount of cyclic siloxane (γ) in the dispersion.On the other hand, from the viewpoint of the availability of organo-modified silicone (α), it is advantageous to allow the presence of cyclic siloxane (γ) as a by-product during the synthesis of the organo-modified silicone (α).Further investigation by the present inventors has revealed that when the amount of cyclic siloxane (γ) in the dispersion is a predetermined amount or less, the process stability of the dispersion, the water absorption resistance (anti-wicking property) of the textile product, and the color of the textile product are improved while maintaining the availability of organo-modified silicone (α).

[0011] In formula (1a), R 20 and R 21 each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms.

[0012] In formula (1a), a is an integer of 30 or less. In one embodiment, a is 3 or more. On the other hand, when a is a predetermined value or less, there is a tendency for adverse effects on the product stability of the dispersion to be reduced. From this viewpoint, a is preferably 30 or less, or 20 or less, or 10 or less.

[0013] In one aspect, the concentration of the cyclic siloxane (γ) in the dispersion is 1,000 ppm by mass or less, preferably 500 ppm by mass or less, or 100 ppm by mass or less, or 10 ppm by mass or less, or 0 ppm by mass, from the viewpoints of antiwicking properties, the color of the textile product, and processing stability (gum-up properties). The amount of the cyclic siloxane (γ) can be confirmed using a GC / MS (gas chromatograph mass spectrometer).

[0014] Methods for adjusting the concentration of the cyclic siloxane (γ) in the dispersion to the above range include carrying out a heating and decompression step or a distillation step during the synthesis of the hydrogen silicone that is the raw material for the organo-modified silicone (α).

[0015] <Organo-modified silicone (α)> The organo-modified silicone (α) is a compound represented by the following general formula (1): [In formula (1), R 20 , R 21 and R 22 each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms; R 23 represents a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 carbon atoms; R 30 , R 31 , R 32 , R 33 , R 34 and R 35 each independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 carbon atoms; a represents an integer of 0 or more, b represents an integer of 1 or more, (a+b) is 10 to 200, and when a is 2 or more, a plurality of R 20 and R 21 may be the same or different, and when b is 2 or more, a plurality of R 22 and R 23 may be the same or different.] In general formula (1), the structural units may be arranged in any of block, random, and alternating configurations.

[0016] In general formula (1), the number of carbon atoms in the hydrocarbon group having 6 to 50 carbon atoms and having an aromatic ring, or the alkyl group having 6 to 100 carbon atoms is preferably 6 to 50, or 16 to 44, or 18 to 42, or 20 to 40 from the viewpoint of initial water repellency and durable water repellency, and is preferably 6 to 50, or 8 to 40, or 8 to 36, or 8 to 24 from the viewpoint of chalk mark resistance.

[0017] In general formula (1), the alkoxy group having 1 to 4 carbon atoms may be linear or branched. More specifically, the alkoxy group having 1 to 4 carbon atoms is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group.

[0018] In the general formula (1), examples of the hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring include an aralkyl group having 6 to 50 carbon atoms, and a group represented by the following general formula (2): [In formula (2), R 40 represents an alkylene group having 2 to 6 carbon atoms; R 41 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and c represents an integer of 0 to 3. When c is 2 or 3, a plurality of R 41 may be the same or different.] or a group represented by the following general formula (3): [In formula (3), R 42 represents an alkylene group having 2 to 6 carbon atoms; R 43 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and d represents an integer of 0 to 3. When d is 2 or 3, a plurality of R 43 may be the same or different.] The alkylene group in the general formulae (2) and (3) may be linear or branched.

[0019] Examples of the aralkyl group having 6 to 50 carbon atoms include a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a naphthylethyl group, etc. Among these, the phenylethyl group and the phenylpropyl group are preferred in terms of ease of industrial production and availability.

[0020] In the group represented by the general formula (2), R 40 is preferably an alkylene group having 2 to 4 carbon atoms, and c is preferably 0 or 1, and more preferably 0.

[0021] In the group represented by the general formula (3), R 42 is preferably an alkylene group having 2 to 4 carbon atoms, and d is preferably 0 or 1, and more preferably 0.

[0022] As the hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, the aralkyl group having 6 to 50 carbon atoms and the group represented by general formula (2) are preferred in that they are easy to produce industrially and are readily available, and the aralkyl group having 6 to 50 carbon atoms is more preferred in that it can improve the water repellency of the resulting textile product.

[0023] The alkyl group having 6 to 100 carbon atoms may be linear or branched. Examples of the alkyl group having 6 to 100 carbon atoms include an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a myristyl group, a cetyl group, a stearyl group, a 1-hexacosenyl group (C26), a 1-octacosenyl group (C28), a 1-triacontenyl group (C30), and a 1-dotriacontenyl group (C32).

[0024] In terms of ease of industrial production and availability, R 20 , R 21 and R 22 are each independently preferably a hydrogen atom or a methyl group, more preferably a methyl group.

[0025] From the viewpoint of initial water repellency and durable water repellency, R 23 is preferably a saturated hydrocarbon having 6 to 50 carbon atoms, and the number of carbon atoms is more preferably 16 to 44, or 18 to 42, or 20 to 40. From the viewpoint of chalk mark resistance, in general formula (1), R 23is preferably a saturated hydrocarbon having 6 to 50 carbon atoms, and more preferably has 8 to 40, or 8 to 36, or 8 to 24 carbon atoms.

[0026] In general formula (1), a is an integer of 0 or more. In terms of ease of industrial production, availability, and superior peel strength of the resulting fiber product against resin coating, a is preferably 40 or less, and more preferably 30 or less.

[0027] In general formula (1), (a+b) is 10 to 200. From the viewpoint of ease of industrial production and availability, (a+b) is preferably 20 to 100, and more preferably 40 to 60. When (a+b) is within the above range, the production and handling of the silicone itself tends to be easier.

[0028] The organo-modified silicone (α) of this embodiment can be synthesized by a conventionally known method, for example, by subjecting a silicone having a SiH group to a hydrosilylation reaction with an aromatic compound having a vinyl group and / or an α-olefin.

[0029] Examples of the silicone having a SiH group include methylhydrogensilicone and a copolymer of dimethylsiloxane and methylhydrogensiloxane, each having a degree of polymerization of 10 to 200. Among these, the copolymer of dimethylsiloxane and methylhydrogensiloxane is preferred from the viewpoint of water repellency.

[0030] The aromatic compound having a vinyl group is represented by R 23 In the above formula, the aromatic compound is a compound from which a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring is derived. Examples of aromatic compounds having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumyl phenyl ether, allyl-o-phenyl phenyl ether, allyl-tri(phenylethyl)-phenyl ether, and allyl-tri(2-phenylpropyl)phenyl ether.

[0031] The above α-olefin is represented by R in the above general formula (1). 23 In the above formula, it is a compound from which an alkyl group having 6 to 100 carbon atoms is derived. Examples of the α-olefin include α-olefins having 6 to 100 carbon atoms such as 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexacosene (C26), 1-octacosene (C28), 1-triacontene (C30), and 1-dotriacontene (C32).

[0032] The hydrosilylation reaction may be carried out by reacting the silicone having a SiH group with the aromatic compound having a vinyl group and the α-olefin in a stepwise or all at once, if necessary, in the presence of a catalyst.

[0033] The amounts of the SiH group-containing silicone, vinyl group-containing aromatic compound, and α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent weight or number average molecular weight of the SiH group-containing silicone, etc.

[0034] Examples of catalysts used in the hydrosilylation reaction include platinum and palladium compounds, with platinum compounds being preferred, such as platinum(IV) chloride.

[0035] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted appropriately. The reaction temperature is, for example, 10 to 200°C, preferably 50 to 150°C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150°C.

[0036] The hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of inert gases include nitrogen and argon. The reaction proceeds without a solvent, but a solvent may also be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0037] <Dispersion Aid> In one embodiment, the dispersion may further contain a dispersion aid. From the viewpoint of ensuring that the organo-modified silicone (α) is present in a well-dispersed state (in one embodiment, an emulsified state) in the dispersion, one or more selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants may be used as the dispersion aid (in one embodiment, the emulsification aid). The content of the dispersion aid is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 1 to 30 parts by mass, per 100 parts by mass of the organo-modified silicone (α). When the content of the dispersion aid is 0.5 parts by mass or more, the dispersion stability of the organo-modified silicone (α) in the dispersion tends to be further improved, and when it is 50 parts by mass or less, the water repellency of textile products treated with the dispersion tends to be further improved.

[0038] A dispersing aid may be used during polymerization or dispersion (emulsification in one embodiment) of the hydrophobic polymer (β), which will be described later. The dispersing aid used may be the same as that used when dispersing (emulsification in one embodiment) the organo-modified silicone (α). The content of the dispersing aid is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the hydrophobic polymer (β). When the content of the dispersing aid is 0.5 parts by mass or more, the dispersion stability of the hydrophobic polymer (β) in the dispersion tends to be further improved, and when it is 50 parts by mass or less, the water repellency of textile products treated with the dispersion tends to be further improved.

[0039] (Cationic Surfactants) Examples of cationic surfactants include monoalkyltrimethylammonium salts having 8 to 24 carbon atoms, dialkyldimethylammonium salts having 8 to 24 carbon atoms, monoalkylamine acetates having 8 to 24 carbon atoms, dialkylamine acetates having 8 to 24 carbon atoms, and alkylimidazoline quaternary salts having 8 to 24 carbon atoms. Among these, from the viewpoints of dispersibility (emulsifying ability in one embodiment) and processing stability, monoalkyltrimethylammonium salts having 12 to 18 carbon atoms and dialkyldimethylammonium salts having 12 to 18 carbon atoms are preferred. Suitable examples of cationic surfactants include stearyltrimethylammonium sulfate and stearyltrimethylammonium chloride.

[0040] These cationic surfactants may be used alone or in combination of two or more.

[0041] (Nonionic Surfactant) Examples of nonionic surfactants include alcohols, polycyclic phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, oils and fats, polypropylene glycol, and alkylene oxide adducts thereof.

[0042] The alcohols include linear or branched alcohols or alkenols having 8 to 24 carbon atoms, and compounds of the following general formula (AL-1): [In the formula, R 51 and R 52 each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkenyl group having 2 to 8 carbon atoms.] Or, a group represented by the following general formula (AL-2): [In the formula, R 53 represents a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkenyl group having 2 to 8 carbon atoms.]

[0043] Examples of polycyclic phenols include monohydric phenols such as phenol and naphthol, which may have a hydrocarbon group having 1 to 12 carbon atoms, their styrene (e.g., styrene, α-methylstyrene, or vinyltoluene) adducts, and their benzyl chloride reaction products. Examples of amines include linear or branched aliphatic amines having 8 to 44 carbon atoms.

[0044] Examples of the amides include straight-chain or branched-chain fatty acid amides having 8 to 44 carbon atoms.

[0045] The fatty acids include straight-chain or branched-chain fatty acids having 8 to 24 carbon atoms.

[0046] Examples of polyhydric alcohol fatty acid esters include condensation products of polyhydric alcohols and carboxylic acids having 2 to 30 carbon atoms (including the carbon atoms of the carboxyl group). Examples of such polyhydric alcohol fatty acid esters include sorbitan esters composed of sorbitan (alcohol) and carboxylic acids having 2 to 30 carbon atoms (including the carbon atoms of the carboxyl group).

[0047] The number of carbon atoms in the carboxylic acid constituting the sorbitan ester is 2 to 30, and preferably 5 to 21. The sorbitan ester may be a monocarboxylic acid ester of sorbitan and one carboxylic acid, a dicarboxylic acid ester of sorbitol and two carboxylic acids, or a tricarboxylic acid ester of sorbitol and three carboxylic acids, and is preferably a monocarboxylic acid ester.

[0048] Sorbitan esters are represented by the following general formula (4): [In formula (4), R 61 represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms; R 64 , R 65 and R 66 are each independently a hydrogen atom, -CO-R 61 , or -(CH2CH2O) e - (R 62 O) f -R 63 (In the formula, R 62represents an alkylene group having 3 or more carbon atoms, and R 63 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, e represents an integer of 2 or more, and f represents an integer of 0 or more.] or a group represented by the following general formula (5): [In formula (5), R 61 represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms; R 64 , R 65 and R 66 are each independently a hydrogen atom, -CO-R 61 , or -(CH2CH2O) e - (R 62 O) f -R 63 (In the formula, R 62 represents an alkylene group having 3 or more carbon atoms, and R 63 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, e represents an integer of 2 or more, and f represents an integer of 0 or more.

[0049] Examples of the compound represented by the general formula (4) or (5) include sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan sesquistearate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan tristearate.

[0050] Examples of fats and oils include vegetable fats, animal fats and oils, vegetable waxes, animal waxes, mineral waxes, and hardened oils.

[0051] In terms of excellent stability of the dispersion containing the organo-modified silicone (α), a combination of a linear or branched alcohol or alkenol having 8 to 24 carbon atoms and a sorbitan ester is more preferred, and a combination of a polyoxyethylene alkyl ether and a sorbitan fatty acid ester is particularly preferred.

[0052] Examples of the alkylene oxide include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,4-butylene oxide, styrene oxide, epichlorohydrin, etc. From the viewpoints of having little effect on water repellency and improving the dispersibility (emulsifiability in one embodiment) of the organo-modified silicone (α) or the hydrophobic polymer (β), ethylene oxide and 1,2-propylene oxide are preferred as the alkylene oxide, and ethylene oxide is more preferred.

[0053] The number of moles of alkylene oxide added is preferably 1 to 200, more preferably 3 to 100, and even more preferably 5 to 50. When the number of moles of alkylene oxide added is within the above range, high levels of water repellency and product stability can be easily obtained.

[0054] The HLB of the nonionic surfactant is preferably 2 to 18, more preferably 2 to 16. From the viewpoint of storage stability of the dispersion, it is more preferable to use two or more nonionic surfactants having different HLBs within the above range in combination. When a nonionic surfactant is used to disperse (emulsify in one embodiment) the organo-modified silicone (α), it is preferable that the HLB be within the above range from the viewpoint of obtaining good dispersibility. On the other hand, when a nonionic surfactant is used to polymerize or disperse the hydrophobic polymer (β), from the viewpoint of forming a good aqueous dispersion, the HLB is preferably 7 to 18, and taking into consideration the dispersion stability of the liquid polymer (during emulsion polymerization) or solid polymer (during dispersion polymerization) in the composition during and after emulsion polymerization or dispersion polymerization, the HLB is more preferably 9 to 15.

[0055] From the viewpoint of obtaining good dispersion stability (emulsion stability in one embodiment) and water repellency of the dispersion, it is more preferable to use a cationic surfactant and a nonionic surfactant in combination.

[0056] <Hydrophobic polymer (β)> From the viewpoint of initial water repellency and durable water repellency, the dispersion preferably further contains a hydrophobic polymer. The hydrophobic polymer may be one or more selected from the group consisting of acrylic polymers and urethane polymers. The pH of the dispersion is preferably 7 or less, more preferably 6 or less, and even more preferably 5 or less.

[0057] [Acrylic Polymer] The acrylic polymer is represented by the following general formula (A-1): [In formula (A-1), R 1 represents a hydrogen atom or a methyl group, and R 2 represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent.], and a structural unit derived from a monomer (A-1) (hereinafter also referred to as component (A1)) represented by the formula:

[0058] The hydrophobic polymer (β) may be composed solely of structural units derived from the above-mentioned component (A1), or may further contain one or more other structural units. At least one structural unit of the hydrophobic polymer (β) or a monomer corresponding to the structural unit (i.e., forming the structural unit) may have a functional group reactive with a crosslinking agent, such as at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. In this case, the durable water repellency of the resulting textile product can be further improved. The isocyanate group may be protected with a blocking agent to form a blocked isocyanate group. When the functional group is an amino group, the texture of the resulting textile product can be further improved.

[0059] (Monomer (A-1)) The component (A1) has a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent. This hydrocarbon group may be linear or branched, may be a saturated or unsaturated hydrocarbon group, and may further have an alicyclic or aromatic ring. Of these, from the viewpoints of water repellency and texture, linear groups are preferred, and linear alkyl groups are more preferred. In this case, the water repellency is more excellent. When the monovalent hydrocarbon group having 12 or more carbon atoms has a substituent, examples of the substituent include one or more of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and a (meth)acryloyloxy group. In this embodiment, in the general formula (A-1) above, R 2 is preferably an unsubstituted hydrocarbon group.

[0060] From the viewpoint of water repellency, the number of carbon atoms in the hydrocarbon group is preferably 12 to 40, more preferably 12 to 30, and even more preferably 12 to 24. It is particularly preferable that the number of carbon atoms in the hydrocarbon group is 12 to 22. When the carbon number is within this range, the water repellency and feel become particularly excellent. A particularly preferable hydrocarbon group is a linear alkyl group having 18 to 22 carbon atoms.

[0061] Examples of the component (A1) include stearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, and behenyl (meth)acrylate.

[0062] In the present disclosure, "(meth)acrylic acid ester" means "acrylic acid ester" or the corresponding "methacrylic acid ester", and has the same meaning as "(meth)acrylic acid", "(meth)acrylamide", etc.

[0063] The component (A1) is preferably a monofunctional (meth)acrylic acid ester monomer having one polymerizable unsaturated group in one molecule.

[0064] The component (A1) may be used alone or in combination of two or more.

[0065] The mass ratio of the component (A1) to the total amount of the monomer components that are the raw materials for the hydrophobic polymer (β) is preferably 60 to 100 mass%, more preferably 70 to 99 mass%, and even more preferably 75 to 98 mass%.

[0066] (Monomer (A-2)) In one embodiment, the acrylic polymer is represented by the following general formula (A-2): [In formula (A-2), R 11 represents a hydrogen atom or a methyl group; R 12 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, Z represents an ester group or an amide group, and W is —CO—R 13 (In the formula, R 13 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, a —NH—CO—NH group, or a group represented by the following formula (A-3): In a preferred embodiment, the component (A1) contains the component (A2) as well as the component (A1).

[0067] In general formula (A-2), R 12 may be linear or branched, may be a saturated or unsaturated hydrocarbon group, and may further have an alicyclic ring.

[0068] In the above formula (A-2), when Z is an ester group, R 12 is preferably a hydrocarbon group having 2 to 4 carbon atoms, and W is preferably a group represented by —NH—CO—NH2 or a group represented by the above formula (A-3). When Z is an amide group, R 12 is a hydrocarbon group having 2 to 4 carbon atoms, and W is —CO—R 13 is a group represented by R 13 It is preferable that the number of carbon atoms is 1 to 2.

[0069] The component (A2) is not particularly limited, but examples thereof include diacetone acrylamide, 2-methylpropenoate [2-(2-oxo-2-imidazolidinyl)ethyl], and N-[2-(2-oxoimidazolidin-3-yl)ethyl]methacrylamide. Among these, from the viewpoint of durable water repellency of textile products, diacetone acrylamide and 2-methylpropenoate [2-(2-oxo-2-imidazolidinyl)ethyl] are preferred as the component (A2).

[0070] The component (A2) may be used alone or in combination of two or more.

[0071] In the acrylic polymer, the ratio of the structural units derived from component (A1) to the structural units derived from component (A2) is preferably (A1) / (A2), the ratio of the mass of component (A1) to the mass of component (A2), from 99.9 / 0.1 to 70 / 30, more preferably from 99.8 / 0.2 to 80 / 20, and even more preferably from 99.7 / 0.3 to 90 / 10. When (A1) / (A2) is within the above range, the durable water repellency and water repellency of the resulting textile product are improved.

[0072] The total mass ratio of the component (A1) and the component (A2) to the total amount of the monomer components that are raw materials for the acrylic polymer is preferably 10 to 100 mass%, more preferably 20 to 95 mass%, and even more preferably 30 to 90 mass%.

[0073] (Reactive activator (B)) In one embodiment, the acrylic polymer can be obtained by emulsion polymerization or dispersion polymerization. In order to improve the emulsion stability in the dispersion of the acrylic polymer after polymerization, it is preferable that the monomer component that is the raw material of the acrylic polymer further contains a reactive activator (B) (hereinafter also referred to as "component (B)"). In other words, it is preferable that the acrylic polymer further contains a structural unit derived from the reactive activator (B). The reactive activator (B) is (B1) an activator having an HLB of 7 to 18 and represented by the following general formula (I-1): [In formula (I-1), R 3 represents a hydrogen atom or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, Y1 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.], (B2) a compound having an HLB of 7 to 18 and represented by the following general formula (II-1): [In formula (II-1), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group; Y 2 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.], and (B3) a compound having an HLB of 7 to 18, in which an alkylene oxide having 2 to 4 carbon atoms is added to an oil or fat having a hydroxyl group and a polymerizable unsaturated group.

[0074] In the present disclosure, the term "reactive activator" refers to a surfactant having radical reactivity, more specifically, a surfactant having one or more polymerizable unsaturated groups in the molecule, which can be copolymerized with a monomer such as a (meth)acrylic acid ester.

[0075] Furthermore, throughout this disclosure, "HLB" refers to Griffin's HLB, which is obtained by modifying Griffin's formula to the following formula: Here, the hydrophilic group refers to an ethylene oxide group. HLB = (hydrophilic group x 20) / molecular weight

[0076] The HLB of the compounds (B1) to (B3) is 7 to 18, and from the viewpoint of emulsion stability in the dispersion during emulsion polymerization or dispersion polymerization of the acrylic polymer of this embodiment and after polymerization (hereinafter simply referred to as emulsion stability), it is preferably 9 to 15. Furthermore, from the viewpoint of storage stability of the dispersion, it is more preferable to use two or more reactive activators (B) having different HLBs within the above range in combination.

[0077] In the reactive activator (B1) represented by the general formula (I-1), R 3 is a hydrogen atom or a methyl group, and is more preferably a methyl group in terms of copolymerizability with the component (A1).

[0078] In general formula (I-1), X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and from the viewpoint of the dispersion (emulsion, in one embodiment) stability of the acrylic polymer of the present embodiment, a linear alkylene group having 2 to 3 carbon atoms is more preferred.

[0079] In general formula (I-1), Y 1 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. 1 The type, combination and number of alkyleneoxy groups in may be appropriately selected so as to fall within the above HLB range. When two or more types of alkyleneoxy groups are used, they may have a block addition structure or a random addition structure.

[0080] The compound represented by the above general formula (I-1) includes compounds represented by the following general formula (I-2): [In formula (I-2), R 3 represents a hydrogen atom or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, A 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms, m is appropriately selected so as to fall within the above HLB range, and in one embodiment, m is an integer of 1 to 80, and when m is 2 or more, m A 1 O may be the same or different.] is preferred.

[0081] In general formula (I-2), R 3 is a hydrogen atom or a methyl group, and is more preferably a methyl group in terms of copolymerizability with the component (A1).

[0082] In general formula (I-2), X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and from the viewpoint of the dispersion (emulsion, in one embodiment) stability of the acrylic polymer of the present embodiment, a linear alkylene group having 2 to 3 carbon atoms is more preferable.

[0083] In general formula (I-2), A 1 O is an alkyleneoxy group having 2 to 4 carbon atoms. 1The types and combinations of O and the number m can be appropriately selected so as to fall within the above HLB range. In terms of the dispersion (emulsion in one embodiment) stability of the acrylic polymer of this embodiment, m is preferably an integer of 1 to 80, and more preferably an integer of 1 to 60. When m is 2 or more, m A 1 O may be the same or different. 1 When there are two or more types of O, they may have a block addition structure or a random addition structure.

[0084] The component (B1) represented by the general formula (I-2) above can be obtained by any conventionally known method, and is not particularly limited. It can also be easily obtained as a commercially available product, such as "Latemul PD-420," "Latemul PD-430," and "Latemul PD-450" manufactured by Kao Corporation.

[0085] In the component (B2) represented by the general formula (II-1) used in this embodiment, R 4 is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group, and examples thereof include a tridecenyl group, a tridecadienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group, and a heptadecatrienyl group. In terms of the dispersion (emulsion in one embodiment) stability of the acrylic polymer of this embodiment, R 4 is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

[0086] Y 2 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. 2 The type, combination, and number of alkyleneoxy groups in the formula (I) can be appropriately selected so as to fall within the above-mentioned HLB range. When two or more types of alkyleneoxy groups are used, they may have a block addition structure or a random addition structure. In terms of the dispersion (emulsion in one embodiment) stability of the acrylic polymer of this embodiment, the alkyleneoxy group is preferably an ethyleneoxy group.

[0087] The compound represented by the general formula (II-1) above is represented by the following general formula (II-2):

[0088] [In formula (II-2), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group, 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms, n can be appropriately selected so as to fall within the above HLB range, and specifically, an integer of 1 to 50 is preferred. When n is 2 or more, n A's are 2 O may be the same or different.] is preferred.

[0089] R in the compound represented by the above general formula (II-2) 4 represents R in the above general formula (II-1). 4 The same can be mentioned.

[0090] A 2 O is an alkyleneoxy group having 2 to 4 carbon atoms. In terms of the dispersion (emulsion in one embodiment) stability of the acrylic polymer of this embodiment, A 2 The types and combinations of O and the number of n can be appropriately selected so as to fall within the above HLB range. 2 O is more preferably an ethyleneoxy group, and n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and even more preferably an integer of 8 to 14. When n is 2 or more, n A 2 O may be the same or different. 2 When there are two or more types of O, they may have a block addition structure or a random addition structure.

[0091] The component (B2) represented by the general formula (II-2) used in this embodiment can be synthesized by adding an alkylene oxide to a phenol having a corresponding unsaturated hydrocarbon group using a conventionally known method, and the method is not particularly limited. For example, it can be synthesized by adding a predetermined amount of alkylene oxide under pressure at 120 to 170°C using an alkali catalyst such as caustic soda or caustic potassium.

[0092] The phenols having the corresponding unsaturated hydrocarbon group include not only pure products or mixtures produced industrially, but also those present as pure products or mixtures extracted and purified from plants, etc. Examples include 3-[8(Z),11(Z),14-pentadecatrienyl]phenol, 3-[8(Z),11(Z)-pentadecadienyl]phenol, 3-[8(Z)-pentadecenyl]phenol, 3-[11(Z)-pentadecenyl]phenol, etc., which are extracted from cashew nut shells, etc. and are collectively known as cardanol.

[0093] The component (B3) used in this embodiment is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group, and the fat or oil has an HLB of 7 to 18. Examples of the fat or oil having a hydroxyl group and a polymerizable unsaturated group include mono- or diglycerides of fatty acids that may contain hydroxyunsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.), and triglycerides of fatty acids containing at least one hydroxyunsaturated fatty acid (ricinoleic acid, ricinoleidic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of dispersion (emulsion in one embodiment) stability of the acrylic polymer of this embodiment, alkylene oxide adducts of triglycerides of fatty acids containing at least one hydroxy unsaturated fatty acid are preferred, alkylene oxide adducts of castor oil (triglycerides of fatty acids containing ricinoleic acid) having 2 to 4 carbon atoms are more preferred, and ethylene oxide adducts of castor oil are even more preferred. Furthermore, the number of moles of alkylene oxide added can be appropriately selected so as to fall within the above-mentioned HLB range, and from the viewpoint of dispersion (emulsion in one embodiment) stability of the acrylic polymer of this embodiment, 20 to 50 moles is more preferred, and 25 to 45 moles is even more preferred. Furthermore, when two or more types of alkylene oxides are used, they may have a block addition structure or a random addition structure.

[0094] The component (B3) used in this embodiment can be synthesized by adding an alkylene oxide to a fat or oil having a hydroxyl group and a polymerizable unsaturated group using a conventionally known method, and is not particularly limited. For example, it can be synthesized by adding a predetermined amount of alkylene oxide to a triglyceride of a fatty acid containing ricinoleic acid, i.e., castor oil, using an alkali catalyst such as caustic soda or caustic potassium under pressure at 120 to 170°C.

[0095] The constituent ratio of the monomer of the component (B) in the acrylic polymer of this embodiment is preferably 0.5 to 20 mass %, more preferably 1 to 15 mass %, and even more preferably 3 to 10 mass %, relative to the total amount of monomer components constituting the acrylic polymer, from the viewpoint of improving the water repellency of the obtained textile product and the emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the acrylic polymer of this embodiment.

[0096] (Monomer (C)) In terms of improving the durable water repellency of the resulting textile product, it is preferable that the acrylic polymer further contains a structural unit derived from at least one monomer (C) (hereinafter also referred to as component (C)) selected from the group consisting of the following (C1), (C2), (C3), and (C4):

[0097] (C1) The following general formula (C-1): [In formula (C-1), R 5 represents hydrogen or a methyl group, R 6 represents a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group, provided that the number of (meth)acryloyloxy groups in the molecule is 2 or less.]

[0098] (C2) The following general formula (C-2): [In formula (C-2), R 7 represents hydrogen or a methyl group, R 8represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent.] (hereinafter, also referred to as component (C2))

[0099] (C3) The following general formula (C-3): [In formula (C-3), R 9 represents an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms.] (hereinafter, also referred to as component (C3))

[0100] (C4) The following general formula (C-4): [In formula (C-4), R 10 represents hydrogen or a methyl group, p represents an integer of 2 or greater, S represents a (p+1)-valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group.]

[0101] The component (C1) is a (meth)acrylic acid ester monomer having a monovalent chain hydrocarbon group having 1 to 11 carbon atoms, which has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group in the ester moiety. In terms of reactivity with a crosslinking agent, the monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. When a textile product is treated with an acrylic polymer having structural units derived from the component (C1) having a group reactive with such a crosslinking agent, the durable water repellency of the resulting textile product can be improved while maintaining its texture. The isocyanate group may be a blocked isocyanate group protected with a blocking agent.

[0102] The chain hydrocarbon group may be linear or branched, and may be a saturated or unsaturated hydrocarbon group. The chain hydrocarbon group may further have a substituent in addition to the functional group. Among these, a linear and / or saturated hydrocarbon group is preferred in terms of improving the durable water repellency of the resulting textile product.

[0103] Specific examples of the component (C1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. These monomers may be used alone or in combination of two or more. Among these, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferred in terms of improving the durable water repellency of the resulting textile product. Furthermore, dimethylaminoethyl (meth)acrylate is preferred in terms of improving the feel of the resulting textile product.

[0104] From the viewpoint of water repellency, the mass of the (C1) component to be blended is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, per 100 parts by mass of the (A1) component to be blended, and from the viewpoint of water repellency, the mass of the (C1) component to be blended is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the (A1) component to be blended.

[0105] The component (C2) is a (meth)acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester moiety. Examples of the cyclic hydrocarbon group include an isobornyl group, a cyclohexyl group, and a dicyclopentanyl group. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. However, when the substituent is a hydrocarbon group, a hydrocarbon group is selected such that the total number of carbon atoms in the substituent and the cyclic hydrocarbon group is 11 or less. Furthermore, from the viewpoint of improving durable water repellency, it is preferable that these cyclic hydrocarbon groups be directly bonded to an ester bond. The cyclic hydrocarbon group may be alicyclic or aromatic, and if alicyclic, it may be a saturated or unsaturated hydrocarbon group. Specific examples of the monomer include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. These monomers may be used alone or in combination of two or more. Among these, isobornyl (meth)acrylate and cyclohexyl methacrylate are preferred, with isobornyl methacrylate being more preferred, in that they can improve the durable water repellency of the resulting textile product.

[0106] The mass of the (C2) component is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the (A1) component, from the viewpoint of water repellency. The mass of the (C2) component is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the (A1) component, from the viewpoint of water repellency.

[0107] The component (C3) is a methacrylic acid ester monomer in which an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester moiety. The chain hydrocarbon group having 1 to 4 carbon atoms is preferably a linear hydrocarbon group having 1 to 2 carbon atoms or a branched hydrocarbon group having 3 to 4 carbon atoms. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. Specific examples of the chain hydrocarbon group include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. These monomers may be used alone or in combination of two or more. Among these, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferred, with methyl methacrylate being more preferred, in terms of improving the durable water repellency of the resulting textile product.

[0108] The mass of the (C3) component is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the (A1) component, from the viewpoint of water repellency. The mass of the (C3) component is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the (A1) component, from the viewpoint of water repellency.

[0109] The component (C4) is a (meth)acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. In this embodiment, polyfunctional (meth)acrylic acid ester monomers having three or more (meth)acryloyloxy groups in one molecule, in which T in the general formula (C-4) is a (meth)acryloyloxy group, are preferred. In the general formula (C-4), the p Ts may be the same or different. Specific examples of the compound include ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. These monomers may be used alone or in combination of two or more. Among these, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferred in terms of improving the durable water repellency of the resulting textile product.

[0110] From the viewpoint of water repellency, the mass of the (C4) component to be blended is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, per 100 parts by mass of the (A1) component to be blended, and from the viewpoint of water repellency, the mass of the (C4) component to be blended is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, per 100 parts by mass of the (A1) component to be blended.

[0111] The mass of the (C) component to be blended is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, per 100 parts by mass of the (A1) component to be blended, from the viewpoint of water repellency. The mass of the (C) component to be blended is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the (A1) component to be blended, from the viewpoint of water repellency.

[0112] (Monomer (VC)) From the viewpoint of peel strength, the acrylic polymer preferably further contains a constituent unit derived from one or more monomers (VC) selected from the group consisting of vinyl chloride and vinylidene chloride (also referred to as "(VC) component" in the present disclosure).

[0113] The (VC) component is preferably vinyl chloride from the viewpoint of maintaining the texture of the textile product.

[0114] The amount of the (VC) component to be blended is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, per 100 parts by mass of the (A1) component to be blended, from the viewpoints of water repellency, durable water repellency, and peel strength. The amount of the (VC) component to be blended is preferably 100 parts by mass or less, and more preferably 75 parts by mass or less, per 100 parts by mass of the (A1) component to be blended, from the viewpoints of water repellency, durable water repellency, and texture.

[0115] (Monomer (D)) The acrylic polymer may further contain a structural unit derived from a monofunctional monomer (D) (hereinafter also referred to as component (D)) copolymerizable with component (A1), within a range that does not impair the effects of the present invention.

[0116] Examples of component (D) include (meth)acryloylmorpholine, (meth)acrylic acid esters having a hydrocarbon group, (meth)acrylic acid, fumaric acid esters, maleic acid esters, fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene, and styrene, and other fluorine-free vinyl monomers other than component (VC). The (meth)acrylic acid esters having a hydrocarbon group may have a substituent on the hydrocarbon group, such as a vinyl group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, or a blocked isocyanate group, or may have a substituent other than a group reactive with a crosslinking agent, such as a quaternary ammonium group, and may have an ether bond, an ester bond, an amide bond, or a urethane bond. Examples of (meth)acrylic acid esters include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and ethylene glycol di(meth)acrylate. Among these, (meth)acryloylmorpholine is more preferred in that it can improve the peel strength of the resulting textile product against the coating.

[0117] The weight-average molecular weight of the acrylic polymer of this embodiment is preferably 30,000 or more. When the weight-average molecular weight is 30,000 or more, the water repellency of the resulting textile product tends to be further improved. Furthermore, the weight-average molecular weight of the acrylic polymer is more preferably 100,000 or more. In this case, the resulting textile product can exhibit more sufficient water repellency. The upper limit of the weight-average molecular weight of the acrylic polymer is preferably about 5,000,000.

[0118] In the present disclosure, the weight-average molecular weight of an acrylic polymer refers to a value measured using a GPC (gel permeation chromatography) device (for example, a GPC "HLC-8020" manufactured by Tosoh Corporation) at a column temperature of 40°C and a flow rate of 1.0 ml / min using tetrahydrofuran as an eluent, and converted into standard polystyrene. The columns used are three TSK-GEL G5000HHR, G4000HHR, and G3000HHR columns manufactured by Tosoh Corporation, connected together.

[0119] The melt viscosity of the acrylic polymer at 105°C is preferably 1000 Pa·s or less. When the melt viscosity at 105°C is 1000 Pa·s or less, the texture of the obtained textile product tends to be easily maintained. Furthermore, when the acrylic polymer has a melt viscosity of 1000 Pa·s or less, when the acrylic polymer is dispersed (emulsified in one embodiment) to form a dispersion, precipitation or sedimentation of the acrylic polymer can be suppressed, and the storage stability of the dispersion tends to be easily maintained. Note that the melt viscosity at 105°C is more preferably 500 Pa·s or less. In this case, the obtained textile product, etc., exhibits sufficient water repellency and also has an excellent texture. From the viewpoint of water repellency, the melt viscosity of the acrylic polymer at 105°C may be, for example, 10 Pa·s or more, 50 Pa·s or more, or 100 Pa·s or more.

[0120] The "melt viscosity at 105°C" is determined by using an elevated flow tester (e.g., Shimadzu CFT-500) to place 1 g of an acrylic polymer in a cylinder equipped with a die (length 10 mm, diameter 1 mm), holding the temperature at 105°C for 6 minutes, and measuring the melt viscosity at 100 kgf / cm using a plunger. 2 This refers to the viscosity when measured under a load of 1000 kJ / cm.

[0121] [Urethane-Based Polymer] Examples of the urethane-based polymer include hydrophobic compounds having a structural unit derived from a polyfunctional compound represented by the following general formula (UI-1) and a structural unit derived from an isocyanate compound represented by the following general formula (UII):

[0122] R U31 [-W 1 -R U32 ] d [-V 1 ] e (UI-1) [In formula (UI-1), d represents an integer of 1 or more, e represents an integer of 2 or more, (d+e) is 3 to 6, and R U31 represents a (d+e) valent organic group, W 1 represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group; R U32 represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms; V1 represents a hydroxy group, an amino group, or a carboxy group, provided that e V 1 two or more of which are hydroxy groups and / or amino groups.

[0123] R U33 [-NCO] f (UII) [In formula (UII), R U33 represents an f-valent organic group, and f represents an integer of 2 to 7.

[0124] Such a hydrophobic compound can be obtained by reacting at least a polyfunctional compound represented by the above general formula (UI-1) with an isocyanate compound represented by the above general formula (UII).

[0125] In the present disclosure, an ester group refers to a group represented by -O-CO-. An amide group refers to a group represented by -NH-CO-. A urethane group refers to a group represented by -O-CO-NH-. A urea group refers to a group represented by -NH-CO-NH-. An isocyanate group refers to a group represented by -N=C=O. A carbonyl group refers to a group represented by -CO-.

[0126] First, the polyfunctional compound represented by the above general formula (UI-1) will be described.

[0127] In the above general formula (UI-1), when d is 2 or more, a plurality of W 1 may be the same or different, and multiple R U32 may be the same or different, and multiple V 1 may be the same or different.

[0128] R U31 represents a (d+e)-valent organic group. From the viewpoint of water repellency, durable water repellency (particularly, washability) and water penetration prevention, R U31 The number of carbon atoms in R is preferably 2 to 40, and more preferably 4 to 12. U31 The compound represented by the following chemical formula (7): a group represented by the following chemical formula (8): and a group represented by the following chemical formula (9): In formula (9), m1 represents an integer of 1 or more.

[0129] From the viewpoint of ease of handling of the polymer, (d+e) is preferably 3 to 4. m1 represents an integer of 1 or more, and is preferably 1 to 3.

[0130] R U31 may be a residue obtained by removing (d+e) functional groups from a polyfunctional organic compound (hereinafter referred to as "polyfunctional compound A") having (d+e) functional groups of at least one type selected from the group consisting of hydroxy groups, amino groups, and carboxy groups, provided that two or more of the (d+e) functional groups are hydroxy groups and / or amino groups.

[0131] Examples of the polyfunctional compound A include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, glycerin, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aminoethylethanolamine, diethanolamine, triethanolamine, etc. Among these, trimethylolpropane, ditrimethylolpropane, diethanolamine, and diethylenetriamine are preferred from the viewpoints of water repellency, durable water repellency (particularly washing resistance), water soak resistance, and dispersion stability of hydrophobic compounds.

[0132] W 1 represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group. 1 is preferably an ester group or a urethane group from the viewpoints of water repellency, durable water repellency (particularly, washability), and water penetration resistance.

[0133] R U32represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms. The hydrocarbon group may be a saturated or unsaturated hydrocarbon group, and may further have an alicyclic or aromatic ring. As the hydrocarbon group, a linear one is preferred, and a linear alkyl group is more preferred, as this will result in better water repellency. The number of carbon atoms in the hydrocarbon group is preferably 10 to 24, more preferably 12 to 22, and particularly preferably 12 to 18. When the carbon number is within this range, the water repellency and feel will be particularly excellent. As the hydrocarbon group, a linear alkyl group having 12 to 18 carbon atoms is particularly preferred.

[0134] R U32 Examples of the alkyl group include nonyl, decyl, undecyl, dodecyl (lauryl), myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, eicosyl, heneicosyl, and behenyl groups.

[0135] R U32 may be a residue obtained by removing the reactive group from a reactive hydrocarbon compound having a reactive group capable of reacting with a functional group possessed by the polyfunctional compound A. Examples of the reactive hydrocarbon compound include higher fatty acids having 8 to 24 carbon atoms (note that the number of carbon atoms includes the carbon of the carbonyl group), higher aliphatic alcohols, higher aliphatic monoisocyanates, and higher aliphatic amines.

[0136] Examples of higher fatty acids include lauric acid, myristic acid, pentadecylic acid, palmitic acid, heptadecanoic acid, stearic acid, oleic acid, eicosanoic acid, and docosanoic acid.

[0137] Examples of higher aliphatic alcohols include lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, stearyl alcohol, oleyl alcohol, eicosanol, heneicosanol, and behenyl alcohol.

[0138] Examples of higher aliphatic monoisocyanates include decyl isocyanate, undecyl isocyanate, dodecyl isocyanate, myristyl isocyanate, pentadecyl isocyanate, cetyl isocyanate, stearyl isocyanate, eicosyl isocyanate, and behenyl isocyanate.

[0139] Examples of higher aliphatic amines include decylamine, laurylamine, myristylamine, stearylamine, and behenylamine.

[0140] V 1 represents a hydroxy group, an amino group, or a carboxy group. 1 is preferably a hydroxy group or an amino group from the viewpoint of durable water repellency.

[0141] The polyfunctional compound represented by the general formula (UI-1) can be prepared by, for example, adding the above-mentioned polyfunctional organic compound (polyfunctional compound A) having (d+e) functional groups of at least one kind selected from the group consisting of hydroxyl groups, amino groups, and carboxyl groups to a compound containing [-W 1 -R U32 The compound can be produced by introducing d hydrophobic groups represented by the following formula:

[0142] [-W 1 -R U32 The hydrophobic group represented by the formula] can be introduced, for example, by reacting 1 mole or more of the reactive hydrocarbon compound with 1 mole of the polyfunctional compound A by a conventionally known synthesis method, i.e., esterification reaction, amidation reaction, or urethane reaction, so that the number e of unreacted functional groups in the polyfunctional compound A is 2 or more.

[0143] The polyfunctional compound represented by the general formula (UI-1) is not particularly limited, but is preferably at least one selected from the group consisting of polyfunctional compounds represented by the following general formula (UI-2), polyfunctional compounds represented by the following general formula (UI-3), and polyfunctional compounds represented by the following general formula (UI-4):

[0144] C[-R 41 ] g [-R 42 -V 2 ]h [-R 43 -W 2 -R 44 ] i (UI-2) [In formula (UI-2), g is an integer of 0 or 1, h is an integer of 2 or 3, i is an integer of 1 or 2, (g+h+i) is 4, and R 41 represents a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R 42 represents a divalent alkylene group having 1 to 2 carbon atoms, R 43 represents a divalent alkylene group having 1 to 4 carbon atoms, R 44 represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms; W 2 represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group; V 2 represents a hydroxy group, an amino group, or a carboxy group. 2 is a hydroxy group and / or an amino group.

[0145] [In formula (UI-3), R 51 and R 52 each independently represents a linear or branched hydrocarbon group having 1 to 4 carbon atoms; R 54 and R 55 each independently represents a divalent alkylene group having 1 to 4 carbon atoms; R 53 , R 56 , R 57 and R 58 each independently represents a monovalent group represented by the following general formula (I-3a) or (I-3b): 59 -V 3 (I-3a) {R 59 represents a divalent alkylene group having 1 to 4 carbon atoms, V 3 represents a hydroxy group, an amino group, or a carboxy group.} -R 60 -W 3 -R 61 (I-3b) {R 60 represents a divalent alkylene group having 1 to 4 carbon atoms, R 61 represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms; W 3represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group.}, where R 53 , R 56 , R 57 and R 58 At least two of them are V 3 is a hydroxy group or an amino group, and is a group represented by the above general formula (I-3a).

[0146] [In formula (UI-4), j represents an integer of 1 to 4, and R 71 and R 73 each independently represents a divalent alkylene group having 1 to 4 carbon atoms; R 72 and R 74 each independently represents a hydroxy group, an amino group, or a monovalent group represented by the following general formula (I-4a), and R 75 represents hydrogen or a monovalent group represented by the following general formula (I-4b), (I-4c) or (I-4d). 4 -R 76 (I-4a) {In formula (I-4a), W 4 represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group; R 76 represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms.} -R 77 -OH (I-4b) {In formula (I-4b), R 77 represents an alkylene group having 2 to 3 carbon atoms.} -R 78 -W 5 -R 79 (I-4c) {In formula (I-4c), R 78 represents an alkylene group having 2 to 3 carbon atoms, and R 79 represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms; W 5 represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group.} -W 6 -R 80 (I-4d) {In formula (I-4d), W 6 represents a carbonyl group or an amide group, R 80 represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms.}, where R 72 , R 74 and j R75 At least two of R are a hydroxy group, an amino group, hydrogen, or a monovalent group represented by the above general formula (I-4b), 72 and R 74 is a hydroxy group or an amino group, R 75 is hydrogen or a monovalent group represented by the above general formula (I-4b).

[0147] In the polyfunctional compound represented by the general formula (UI-2), when i is 2, a plurality of W 2 When i is 2, a plurality of R 43 When i is 2, a plurality of R 44 may be the same or different. 44 represents R in the above general formula (UI-1). U32 There are multiple R 42 may be the same or different. 2 may be the same or different.

[0148] In the polyfunctional compound represented by the general formula (UI-2), W 2 is a divalent group which is an ester group, an amide group, a urethane group, or a urea group. 2 is preferably an ester group or a urethane group from the viewpoints of water repellency, durable water repellency (particularly, washability) and water penetration resistance.

[0149] In the polyfunctional compound represented by the general formula (UI-2), V 2 is a hydroxy group, an amino group, or a carboxy group. 2 is preferably a hydroxy group or an amino group from the viewpoint of durable water repellency.

[0150] In the group represented by the general formula (I-3a), V 3 is a hydroxy group, an amino group, or a carboxy group. 3 is preferably a hydroxy group or an amino group from the viewpoint of durable water repellency.

[0151] In the group represented by the general formula (I-3b), R 61is a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms. 61 represents R in the above general formula (UI-1). U32 Corresponds to.

[0152] In the group represented by the general formula (I-3b), W 3 is a divalent group which is an ester group, an amide group, a urethane group, or a urea group. 3 is preferably an ester group or a urethane group from the viewpoints of water repellency, durable water repellency (particularly, washability), and water penetration resistance.

[0153] In the group represented by the general formula (I-4a), R 76 is a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms. 76 represents R in the above general formula (UI-1). U32 Corresponds to.

[0154] In the group represented by the general formula (I-4a), W 4 is a divalent group which is an ester group, an amide group, a urethane group, or a urea group. 4 is preferably an ester group, an amide group or a urethane group from the viewpoints of water repellency, durable water repellency (particularly, washability) and water soak resistance.

[0155] In the group represented by the general formula (I-4b), R 79 is a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms. 79 represents R in the above general formula (UI-1). U32 Corresponds to.

[0156] In the group represented by the general formula (I-4c), W 5 is a divalent group which is an ester group, an amide group, a urethane group, or a urea group. 5 is preferably an ester group, an amide group or a urethane group from the viewpoints of water repellency, durable water repellency (particularly, washability) and water soak resistance.

[0157] In the group represented by the general formula (I-4d), R 80 is a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms. 80represents R in the above general formula (UI-1). U32 Corresponds to.

[0158] Next, the isocyanate compound represented by the above general formula (UII) will be described.

[0159] R U33 represents an f-valent organic group. U33 The number of carbon atoms in R is preferably 4 to 40, more preferably 6 to 18, from the viewpoints of water repellency, durable water repellency (particularly, washability) and water soak resistance. U33 f may be an integer of 2 to 7, and is preferably 2 to 3 from the viewpoints of water repellency, durable water repellency (particularly, washability) and water soak resistance.

[0160] The isocyanate compound represented by the general formula (UII) may be a polyisocyanate compound. Examples of the polyisocyanate compound include diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate (MDI), liquid MDI typified by polyphenyl polymethyl polyisocyanate, crude MDI, hexamethylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and isophorone diisocyanate, as well as trimers of these isocyanurate rings. Among these, hexamethylene diisocyanate is preferred from the viewpoints of water repellency, durable water repellency (particularly, washing resistance), and water penetration resistance.

[0161] Examples of the hydrophobic compound obtained by reacting the polyfunctional compound represented by the general formula (UI-1) with the isocyanate compound represented by the general formula (UII) include hydrophobic compounds having a partial structure represented by the following general formula (UIIII-1), general formula (UIIII-2), or general formula (UIIII-3).

[0162] [In formula (UIII-1), n1 represents an integer of 2 or more, R 91 and R 92 each independently represents a linear or branched monovalent hydrocarbon group having 10 to 24 carbon atoms.

[0163] n1 represents an integer of 2 or more, and is preferably an integer of 2 to 100, more preferably 2 to 50, from the viewpoints of water repellency, durable water repellency (particularly washability), resistance to water penetration, dispersion stability of the hydrophobic compound, and ease of handling of the polymer.

[0164] [In formula (UIII-2), n2 represents an integer of 2 or more, n3 represents an integer of 1 or more, and R 93 each independently represents a linear or branched monovalent hydrocarbon group having 10 to 24 carbon atoms.

[0165] n2 represents an integer of 2 or more, and is preferably an integer of 2 to 200, more preferably 2 to 100, from the viewpoints of water repellency, durable water repellency (particularly washability), resistance to water penetration, dispersion stability of the hydrophobic compound, and ease of handling of the polymer.

[0166] n3 represents an integer of 1 or more, and is preferably 1 to 3, more preferably 1, from the viewpoints of water repellency, durable water repellency (particularly washability), water soak resistance, and dispersion stability of the hydrophobic compound.

[0167] [In formula (UIII-3), n4 represents an integer of 2 or more, and R 94 each independently represents a linear or branched monovalent hydrocarbon group having 10 to 24 carbon atoms.

[0168] n4 represents an integer of 2 or more, and is preferably an integer of 2 to 200, more preferably 2 to 100, from the viewpoints of water repellency, durable water repellency (particularly washability), resistance to water penetration, dispersion stability of the hydrophobic compound, and ease of handling of the polymer.

[0169] Examples of hydrophobic compounds having the partial structure represented by the above general formula (UIII-1) include compounds represented by the following formula (UIII-4):

[0170] [In formula (UIII-4), n5 represents an integer of 2 or more, and R X is represented by the following formula (R-1):

[0171] represents a monovalent organic group represented by the following formula:

[0172] n5 represents an integer of 2 or more, and is preferably from 2 to 100, more preferably from 2 to 50, from the viewpoints of water repellency, durable water repellency (particularly washability), resistance to water penetration, dispersion stability of the hydrophobic compound, and ease of handling of the polymer.

[0173] Examples of hydrophobic compounds having the partial structure represented by the above general formula (UIII-2) include compounds represented by the following formula (UIII-5):

[0174] [In formula (UIII-5), n6 represents an integer of 2 or more, and n7 represents an integer of 1 or more. R X represents a monovalent organic group represented by the above formula (R-1).

[0175] n6 represents an integer of 2 or more, and is preferably an integer of 2 to 200, more preferably 2 to 100, from the viewpoints of water repellency, durable water repellency (particularly washability), resistance to water penetration, dispersion stability of the hydrophobic compound, and ease of handling of the polymer.

[0176] n7 represents an integer of 1 or more, and is preferably 1 to 3, more preferably 1, from the viewpoints of water repellency, durable water repellency (particularly washability), water penetration resistance, and dispersion stability of the hydrophobic compound.

[0177] Examples of hydrophobic compounds having the partial structure represented by general formula (UIII-3) above include compounds represented by formula (UIII-6) below.

[0178] [In formula (UIII-6), n8 represents an integer of 2 or more, R X represents a monovalent organic group represented by the above formula (R-1).

[0179] n8 represents an integer of 2 or more, and is preferably from 2 to 200, more preferably from 2 to 100, from the viewpoints of water repellency, durable water repellency (particularly washability), resistance to water penetration, dispersion stability of the hydrophobic compound, and ease of handling of the polymer.

[0180] From the viewpoint of chemical resistance, the hydrophobic compound according to this embodiment preferably has a blocked isocyanate group protected with a blocking agent. From the viewpoint of chemical resistance, the ratio of the blocked isocyanate groups to the total number of isocyanate groups and blocked isocyanate groups contained in the hydrophobic compound is preferably 80% or more, more preferably 90% or more, and even more preferably 100%.

[0181] Examples of blocked isocyanate groups protected with a blocking agent include groups represented by the following general formula: (—NH—CO—B) [wherein B is a group derived from the blocking agent].

[0182] Examples of blocking agents include pyrazoles such as 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4-bromopyrazole, and pyrazole; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and tert-butyl alcohol; phenols such as phenol, methylphenol, chlorophenol, p-isobutylphenol, p-tert-butylphenol, p-isoamylphenol, p-octylphenol, and p-nonylphenol; Examples of the blocking agent include active methylene compounds such as dimethyl malonate, diethyl malonate, acetylacetone, methyl acetoacetate, and ethyl acetoacetate; oximes such as formaldoxime, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; lactams such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam; N-substituted amides such as N-methylacetamide and acetanilide; imide compounds such as succinimide and phthalimide; and imidazole compounds such as imidazole and 2-methylimidazole. One type of blocking agent may be used alone, or two or more types may be used in combination. Among these, from the viewpoints of versatility, reactivity of the blocked isocyanate group, and ease of blocking, it is preferable to use at least one compound selected from the group consisting of pyrazoles, oximes, and lactams, and it is more preferable to use at least one compound selected from the group consisting of dimethylpyrazole, methyl ethyl ketone oxime, and caprolactam.

[0183] The weight-average molecular weight (Mw) of the hydrophobic compound of the present embodiment may be preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 2,000 to 20,000, from the viewpoints of water repellency, durable water repellency (particularly washability), water soak resistance, and dispersion stability of the hydrophobic compound. The weight-average molecular weight of the hydrophobic compound is measured by GPC (gel permeation chromatography) and is a value converted into standard polystyrene.

[0184] The amount of the compound represented by general formula (UII) blended when reacting a polyfunctional compound represented by general formula (UI-1) having e hydroxy groups and / or amino groups with a compound represented by general formula (UII) is preferably (0.8 to 1.20) x 2 / e mol, more preferably (0.80 to 0.99) x 2 / e mol, and even more preferably (0.85 to 0.95) x 2 / e mol, relative to 1 mol of the polyfunctional compound represented by general formula (UI-1), or more preferably (1.01 to 1.20) x 2 / e mol, and even more preferably (1.05 to 1.15) x 2 / e mol.

[0185] In the dispersion, the amount of the hydrophobic polymer (β) relative to 100 parts by mass of the total of the organo-modified silicone (α) and the hydrophobic polymer (β) is preferably 1 part by mass or more, or 5 parts by mass or more, or 10 parts by mass or more, from the viewpoints of initial water repellency and durable water repellency, and is preferably 99 parts by mass or less, or 95 parts by mass or less, or 90 parts by mass or less, from the viewpoints of initial water repellency and durable water repellency.

[0186] <Liquid Medium> In a typical embodiment, the dispersion contains a liquid medium. In a typical embodiment, the liquid medium contains water and optionally further contains an organic solvent. In one embodiment, the ratio of water to the total liquid medium (100 mass%) is 50 mass% or more. The amount of liquid medium in the dispersion may be adjusted so that the content of the organo-modified silicone (α) and any other components in the dispersion falls within a desired range.

[0187] [Poorly Water-Soluble Organic Solvent] In one embodiment, the dispersion contains, as a liquid medium, an organic solvent (also referred to in the present disclosure as a poorly water-soluble organic solvent) in which the amount of water required to dissolve 1 g of organic solvent at 20°C is greater than 10 mL. In one embodiment, the amount of water required to dissolve 1 g of the organic solvent is greater than 30 mL, preferably greater than 100 mL, and more preferably greater than 1000 mL. Such poorly water-soluble organic solvents contribute to the stable dispersion of the organo-modified silicone (α) (for example, the formation of an emulsion in which the organo-modified silicone (α) is stably dispersed), and therefore contribute to the formation of a dispersion with excellent storage stability. The amount of water required to dissolve 1 g of the organic solvent is a value measured in accordance with JIS K8001:2017 by the following method.

[0188] According to JIS K8001:2017 3.2 "Terminology Depicting the Degree of Dissolution," 1 g of organic solvent is placed in a certain amount of water and shaken vigorously for 30 seconds every 5 minutes at 20°C ± 5°C. The dissolution rate is evaluated as the volume (mL) of water required for dissolution within 30 minutes. In this measurement, 1 mL, 10 mL, 30 mL, 100 mL, or 1000 mL of water is used as the certain amount of water, and whether 1 g of organic solvent dissolves within 30 minutes under the above conditions is examined. The evaluation criteria are as follows: (Evaluation criteria for the amount of water required to dissolve 1 g of organic solvent) 1 mL or less: Dissolved in 1 mL of water within 30 minutes. More than 1 mL and up to 10 mL: Not dissolved in 1 mL of water within 30 minutes, but dissolved in 10 mL of water within 30 minutes. More than 10 mL and up to 30 mL: Not dissolved in 10 mL of water within 30 minutes, but dissolved in 30 mL of water within 30 minutes. More than 30 mL and up to 100 mL: Did not dissolve in 30 mL of water within 30 minutes, but dissolved in 100 mL of water within 30 minutes. More than 100 mL and up to 1000 mL: Did not dissolve in 100 mL of water within 30 minutes, but dissolved in 1000 mL of water within 30 minutes. More than 1000 mL: Did not dissolve in 1000 mL of water within 30 minutes.

[0189] Examples of the amount of water required to dissolve 1 g of organic solvent are as follows: Isoparaffin (isoparaffin having 10 to 16 carbon atoms): more than 1,000 mL Mineral oil (kinematic viscosity at 30°C: 20 mm 2 / s): More than 1000 mL Mineral spirits (boiling point: 180-200°C): More than 1000 mL Ester (2,2,4-trimethyl-1,3-pentanediol diisobutyrate): More than 1000 mL Tripropylene glycol (TPG): 1 mL or less Dipropylene glycol (DPG): 1 mL or less Butyl diglycol: 1 mL or less

[0190] Without being bound by theory, it is presumed that when the organo-modified silicone (α) is dispersed in a water-containing medium in producing a dispersion (in one embodiment, when an emulsion containing the organo-modified silicone (α) is formed), the poorly water-soluble organic solvent promotes the dispersion of the organo-modified silicone (α) (in one embodiment, O / W emulsion), thereby contributing to improving the dispersion stability (in one embodiment, emulsion stability) of the organo-modified silicone (α) in the water-containing medium.

[0191] The poorly water-soluble organic solvent preferably has a structure composed of carbon and hydrogen (i.e., a hydrocarbon structure) in the molecule, in view of the effect of improving the dispersion stability of the organo-modified silicone (α). From this viewpoint, preferred poorly water-soluble organic solvents include, for example, esters (specific examples include 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, ethyl acetate, butyl acetate, butyl glycol acetate, etc.), ketones (specific examples include methyl isobutyl ketone), ethers (specific examples include dibutyl diglycol, diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethyl methyl ... The organic solvent may be, for example, propylene glycol mono-2-ethylhexyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, etc.), alcohols (specific examples include 1-butanol, 1-pentanol, isooctanol, etc.), aromatic solvents (specific examples include toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), or petroleum solvents (specific examples include isoparaffin, mineral oil, mineral spirits, synthetic oils such as poly-α-olefins, etc.), and these organic solvents may be used alone or in combination of two or more.

[0192] The number of carbon atoms in the isoparaffin is preferably 4 or more, more preferably 9 to 20. Examples of such isoparaffins include IP Solvent IP-2028 (isoparaffin having 10 to 16 carbon atoms, manufactured by Idemitsu Kosan Co., Ltd.).

[0193] As the mineral oil, a kinematic viscosity of 50 mm at 30°C is used. 2Examples of suitable mineral oils include mineral oils with a kinematic viscosity of 1 / s or less, more specifically normal undecane, normal dodecane, normal tridecane, normal tetradecane, paraffin, etc. The kinematic viscosity is a value measured according to JIS K 2283:2000. The paraffin may have, for example, 10 to 16 carbon atoms. The mineral oils may be used alone or in combination of two or more. When two or more types are combined, it is preferable that they are mutually compatible. The mineral oil may be a commercially available product, such as Cactus Normal Paraffin N-12D, Cactus Normal Paraffin YHNP, or Cactus Normal Paraffin N-14 (all available from ENEOS Corporation).

[0194] Mineral spirits with a boiling point of 130 to 230°C are particularly preferred.

[0195] From the viewpoint of dispersion stability of the organo-modified silicone (α), the amount of the poorly water-soluble organic solvent in the dispersion is preferably 0.5 to 500 parts by mass, more preferably 1 to 400 parts by mass, even more preferably 1 to 300 parts by mass, and particularly preferably 1 to 200 parts by mass, per 100 parts by mass of the organo-modified silicone (α). The amount of the poorly water-soluble organic solvent is preferably in the above range, since the storage stability and water repellency of the dispersion are good.

[0196] <Water-soluble organic solvent> The dispersion of this embodiment may further contain a water-soluble organic solvent in addition to the poorly water-soluble organic solvent as a liquid medium. In the present disclosure, the water-soluble organic solvent refers to an organic solvent for which the amount of water required to dissolve 1 g of the organic solvent at 20°C is 10 mL or less, as evaluated by the above-mentioned method in accordance with JIS K8001:2017. Examples of the water-soluble organic solvent include dipropylene glycol, tripropylene glycol, butyl diglycol, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, and tetrahydrofuran, with dipropylene glycol, tripropylene glycol, and butyl diglycol being particularly preferred.

[0197] <Additional Components> The dispersion of this embodiment may contain additional components. Examples of the additional components include additional water- and / or oil-repellent components, initiators, chain transfer agents, antislip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, and antifoaming agents. Examples of the additional water- and / or oil-repellent components include waxes (e.g., paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, etc.), animal and vegetable waxes, and mineral waxes.

[0198] The total concentration of the organo-modified silicone (α) and the hydrophobic polymer (β) in the dispersion (the concentration of the organo-modified silicone (α) alone when the hydrophobic polymer (β) is not used) may be changed appropriately depending on the application, but may be, for example, 0.01 to 70% by mass, or 0.05 to 50% by mass. The concentration of the above <additional component> in the dispersion may be changed appropriately depending on the application, but may be, for example, 20% by mass or less, or 5% by mass or less.

[0199] <Method for Producing Dispersion> One aspect of the present invention provides a method for producing the dispersion of the present disclosure. In one aspect, the dispersion may be obtained by mixing an organo-modified silicone (α) with a liquid medium. In one aspect, the method for producing the dispersion includes a mixing step of mixing an emulsion containing the organo-modified silicone (α) with a hydrophobic polymer (β). In one aspect, the method for producing the dispersion includes a polymerization step of polymerizing a monomer component, which is a raw material for the hydrophobic polymer (β), in the presence of the organo-modified silicone (α) (for example, in the presence of an emulsion containing the organo-modified silicone (α)), to obtain the dispersion.

[0200] The emulsion containing organo-modified silicone (α) may contain organo-modified silicone (α), a dispersing aid, and a liquid medium. The content of organo-modified silicone (α) in the emulsion is preferably 1% by mass or more, or 5% by mass or more, or 15% by mass or more, and preferably 70% by mass or less, or 50% by mass or less, or 30% by mass or less. In one aspect, the emulsion containing organo-modified silicone (α) can be used as is as the dispersion of this embodiment.

[0201] <Uses of Dispersion> Uses of the dispersion of the present embodiment include various treatment agents such as surface treatment agents, water repellents, oil repellents, water and oil repellents, antifouling agents, stain removers, release agents, and mold release agents.

[0202] <Method for manufacturing a textile product> One aspect of the present invention provides a textile product treated with the dispersion of the present disclosure (more specifically, obtained by treating fibers with the dispersion of the present disclosure). Another aspect of the present invention also provides a method for manufacturing a textile product, comprising a step of treating a substrate (more specifically, fibers) with the dispersion of the present disclosure.

[0203] <Substrate> Examples of substrates to be treated with the dispersion of the present disclosure include various fiber structures (for example, fabrics, paper, etc., used as filters, electrodes, supports, etc.), stone, etc. Examples of fibers contained in the fiber structures include: natural fibers of animal and plant origin, such as cotton, linen, wool, and silk; synthetic fibers, such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic or recycled fibers, such as rayon and acetate; inorganic fibers, such as glass fiber, carbon fiber, and asbestos fiber; and mixed fibers thereof (for example, mixed and intertwined yarns). The fabric may be a woven fabric, knitted fabric, or nonwoven fabric. The substrate may be a fiber, yarn, or intermediate fiber product (for example, sliver or roving) before being made into a fabric. The dispersion of this embodiment is particularly suitable for imparting water repellency and / or oil repellency to synthetic fibers.

[0204] Examples of natural fibers include cellulosic fibers such as cotton, flax, and pulp, as well as chitin, chitosan, wool, and silk. The pulp may be, for example, wood pulp. Specific examples of wood pulp include mechanical pulps such as ground wood pulp (GP), pressure-raised ground wood pulp (PGW), and thermomechanical pulp (TMP); chemical pulps such as high-yield unbleached softwood kraft pulp (HNKP; N wood), bleached softwood kraft pulp (NBKP; N wood, NB wood), unbleached hardwood kraft pulp (LUKP; L wood), and bleached hardwood kraft pulp (LBKP; L wood); recycled paper pulps such as deinking pulp (DIP) and waste pulp (WP); and semi-chemical pulp (CP).

[0205] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymer polyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupra, polynosic rayon, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0206] The substrate may be leather, and the dispersion may be applied to the leather, for example as an aqueous emulsion, at various stages of leather processing, for example at the wet processing stage of the leather, or at the finishing stage of the leather, in order to make the leather water- and / or oil-repellent.

[0207] The substrate may be paper. The dispersion may be applied to a preformed paper product, or the dispersion may be applied at various stages of papermaking, such as during the paper drying process. Examples of paper products include paper made from bleached or unbleached chemical pulp (e.g., kraft pulp or sulfite pulp), bleached or unbleached high-yield pulp (e.g., groundwood pulp, mechanical pulp, or thermomechanical pulp), recycled paper pulp (e.g., recycled newspaper, recycled magazine, recycled corrugated cardboard, or deinked recycled paper), paper containers, and molded articles. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-grade paper, general liner, medium, neutral white roll paper, neutral liner, anti-corrosion liner, 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, neutral information paper, and molded paper (molded containers).

[0208] For example, when using a woven fabric or knitted fabric (hereinafter also referred to as a woven or knitted fabric), fibers may be woven or knitted to obtain a green machine, and the green machine may then be optionally post-processed to obtain a substrate. The green machine may be obtained using a known loom or knitting machine. Conventional pre-processing and / or post-processing may be performed during weaving or knitting. Examples of post-processing include scouring and relaxation. For example, the green machine may be scoured and relaxed at 80°C to 130°C using a continuous or batch method. Scouring and relaxation using a batch method at 100°C or less is preferred, and the use of a high-pressure liquid jet dyeing machine equipped with a jet nozzle is particularly preferred. After scouring and relaxation, the woven or knitted fabric may be preset. Presetting may be a dry heat treatment using a pin tenter, for example, at 170°C to 200°C for 30 to 120 seconds. After presetting, dyeing may be performed using a conventional procedure, followed by final setting if necessary. A substrate can be obtained using the above procedure.

[0209] <Substrate Treatment with Dispersion> A textile product can be obtained by treating a substrate with the dispersion of this embodiment. The term "treatment" refers to applying the dispersion to a substrate by immersion, spraying, coating, or the like. The dispersion may be applied to the substrate as is, or in the form of a treatment liquid, which is a combination of the dispersion and other components (e.g., an additional liquid medium, various additives, etc.). Since the cyclic siloxane (γ) concentration in such a treatment liquid is further reduced compared to the dispersion, the treatment liquid also provides the same advantages as the dispersion of this embodiment. Through treatment, the polymer, which is the active ingredient of the dispersion, penetrates into the substrate and / or adheres to the surface of the substrate. The dispersion may be applied to the surface of the substrate by a known method such as immersion, spraying, or foam coating, and then dried. For example, the dispersion may be brought into contact with the substrate by padding, spraying, kiss roll coating, slit coating, or the like. Alternatively, the dispersion may be applied to the substrate by a cleaning method, such as laundry application or dry cleaning. The substrate to which the dispersion is attached may be subjected to a dry heat treatment. The dry heat conditions may be, for example, 105°C to 190°C and 30 seconds to 150 seconds. The substrate after dry heat treatment may be subjected to a calendaring process to further improve water repellency. The textile product has a substrate and a dispersion-derived component adhered to the surface and / or interior of the substrate. The dispersion-derived component includes an organo-modified silicone (α) and may optionally further include a hydrophobic polymer (β) and / or a cyclic siloxane (γ).

[0210] The substrate treated with the dispersion may be dried and cured, preferably by heating, to develop water and oil repellency. Curing may be performed by applying the dispersion together with an appropriate crosslinking agent. The heating temperature may be, for example, 100°C to 200°C, or 100°C to 170°C, or 100°C to 120°C. The dispersion of this embodiment provides good performance even when heated at a low temperature (e.g., 100°C to 140°C). The heating time may be, for example, 5 seconds to 60 minutes, or 30 seconds to 3 minutes.

[0211] <Pretreatment of Substrate> The substrate may be pretreated before being treated with the dispersion of the present disclosure. This pretreatment can impart excellent fastness to the textile product after treatment with the dispersion. Pretreatments include: cationization treatment by reacting a reactive quaternary ammonium salt with the substrate; anionization treatment such as sulfonation, carboxylation, or phosphate; and treatments after the anionization treatment such as acetylation, benzoylation, carboxymethylation, grafting, tannic acid treatment, or polymer coating treatment.

[0212] Any of the above-mentioned substrates can be used as the substrate to be pretreated. From the viewpoint of improving the water repellency of the substrate after pretreatment, the substrate to be pretreated is preferably a fiber containing polyamide and / or polyester, and particularly preferably nylon such as nylon 6 or nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate or polylactic acid, or a mixed fiber containing these.

[0213] The pretreatment method is not limited, and a conventionally known method may be used. The pretreatment liquid may be dispersed and diluted in an organic solvent and / or water as necessary, and then applied to the substrate by a known method such as immersion, spraying, or foam application, followed by drying. The pH, temperature, etc. of the pretreatment liquid may be adjusted depending on the desired degree of pretreatment.

[0214] More specifically, such pretreatment can provide a substrate containing at least one type of functional group (hereinafter sometimes referred to as a "specific functional group"), for example, by the following methods: (1) A method of attaching a compound having a specific functional group to a substrate. For example, the substrate may be functionalized with a treatment agent containing a compound having a specific functional group (hereinafter referred to as a functionalizing treatment agent). As long as the treated substrate has a sufficient amount of the specific functional group, a portion of the compound may chemically bond to the substrate. (2) A method of directly preparing a substrate having a specific functional group.

[0215] The specific functional group is, for example, —SO3M 1 (In the formula, M 1 is a monovalent cation. 2 (In the formula, M 2is a monovalent cation), and —O—P(O)(OX 1 ) (OX 2 ) (wherein, X 1 and X 2 are each independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms). 1 , and M 2 Each of X may be, for example, H, K, Na, or an ammonium ion which may have a substituent. 1 , and X 2 In each of the above, when it is an alkyl group, the number of carbon atoms is preferably 1 to 22, or 4 to 12.

[0216] Above -SO3M 1 An example of a compound having the following general formula: [In the formula, X 2 is a hydrogen atom, -SO3M 3 (In the formula, M 3 represents a hydrogen atom or a monovalent cation), a hydroxyphenylsulfonyl group, or a group represented by the following general formula: (In the formula, M 4 represents a hydrogen atom or a monovalent cation), and n is an integer of 3 to 500. ] The weight percentage of SO3 in the above compound is preferably 0.5% or more, or 3% or more, or 5% or more, and preferably 40% or less, or 30% or less, or 20% or less. 3 and M 4 may be H, K, Na, or an ammonium ion which may have a substituent. 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, or a formalin condensate of phenolsulfonic acid and bisphenol S, or a formalin condensate of sulfonated bisphenol S and bisphenol S, or a formalin condensate of phenolsulfonic acid and phenol.

[0217] Above - COOM 2Examples of compounds having the formula include polycarboxylic acid polymers. The polycarboxylic acid polymer may be a polymer obtained by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer. In addition to the above-mentioned monomers, monomers copolymerizable with the monomers may also be used. Examples of copolymerizable monomers include ethylene, vinyl monomers (vinyl chloride, vinyl acetate, etc.), acrylamide, acrylates, and methacrylates. Examples of acrylates and methacrylates include compounds having a hydrocarbon group having 1 to 3 carbon atoms, which may have a substituent such as a hydroxyl group (e.g., methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate). These copolymerizable monomers may be used alone or in combination of two or more.

[0218] A method for producing a polycarboxylic acid polymer includes adding a radical polymerization initiator to an aqueous solution of the above-mentioned monomer and / or its salt (and optionally a monomer copolymerizable with the monomer) and heating the reaction at 30°C to 150°C for 2 to 5 hours. The aqueous solution of the above-mentioned monomer and / or its salt may contain an aqueous solvent, such as an alcohol such as methanol, ethanol, or isopropyl alcohol, or acetone. 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. A chain transfer agent (e.g., octyl thioglycolate) may also be added to adjust the degree of polymerization during radical polymerization. The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized with a neutralizing agent such as an alkali metal or an amine compound. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0219] The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000, in that the resulting textile product has good water repellency.

[0220] The polycarboxylic acid polymer may be a commercially available product such as "Neocrystal 770" (trade name, manufactured by Nicca Chemical Co., Ltd.) or "Ceropol PC-300" (trade name, manufactured by Sanyo Chemical Industries, Ltd.).

[0221] The above -O-P(O)(OX 1 ) (OX 2 ) is, for example, a compound having the following general formula: [In the formula, X 1 and X 2 is as defined above, and X 3represents an alkyl group having 1 to 22 carbon atoms.] Examples of the phosphate ester compound include a phosphate monoester in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, a phosphate diester in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, a phosphate triester in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof. From the viewpoint of the water repellency of the resulting textile product, lauryl phosphate and decyl phosphate are particularly preferred.

[0222] The phosphate ester compound may be a commercially available product such as "Phosphanol ML-200" (trade name, manufactured by Toho Chemical Industry Co., Ltd.).

[0223] The functionalizing treatment agent may be used, for example, as an aqueous solution. Such a functionalizing treatment solution may contain, as necessary, an acid, an alkali, a surfactant, a chelating agent, etc. The functionalizing treatment solution may further contain a salt, for example, to effectively adsorb a compound having a specific functional group to a substrate by a salting-out effect. Examples of such salts include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate. The functionalizing treatment solution may be used to treat a substrate, for example, by padding, immersion, spraying, or coating. Examples of padding treatments include methods using padding devices described in "Textile Dyeing and Processing Dictionary" (published in 1963 by Nikkan Kogyo Shimbun, pp. 396-397) and "Color Dyeing Chemistry III" (published in 1975 by Jikkyo Publishing Co., Ltd., pp. 256-260). Examples of coating treatments include methods using coating machines described in "Dyeing and Finishing Equipment Directory" (published in 1981 by Sen'i-sha, pp. 473-477). The immersion treatment may be carried out using a batch dyeing machine as described in "Dyeing and Finishing Machinery Directory" (published by Sen'i-sha in 1981, pages 196-247). Examples of dyeing machines that can be used include liquid jet dyeing machines, air jet dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, and cheese dyeing machines. Examples of spray treatment include an air sprayer that sprays a pretreatment liquid in the form of a mist using compressed air, or a hydraulic atomization air sprayer.

[0224] The concentration of the functionalization treatment solution, the functionalization treatment conditions, the conditions for the heat treatment after the functionalization treatment, and the like may be adjusted appropriately depending on the purpose. For example, the immersion temperature in the functionalization treatment solution may be 60°C to 130°C, and the immersion treatment time may be 5 to 60 minutes. The pH of the functionalization treatment solution is preferably adjusted to 3 to 5. A pH adjuster such as acetic acid or malic acid may be used to adjust the pH. After the functionalization treatment, it is preferable to remove excess compounds having specific functional groups by washing with water or the like. By thoroughly removing them, the inhibition of water repellency due to treatment with the dispersion of the present disclosure can be suppressed, and the texture of the resulting textile product will be improved. When the functionalization treatment solution contains a solvent such as water, it is preferable to dry the functionalized substrate to remove the solvent such as water. The drying method is not particularly limited and may be either a dry heat method or a wet heat method. The drying temperature and drying time are also not particularly limited and may be, for example, from room temperature to 200°C and from 10 seconds to several days. If necessary, after drying, the film may be subjected to a heat treatment at 100° C. to 180° C. for about 10 seconds to 5 minutes.

[0225] When the substrate is dyed, the functionalization treatment may be carried out before dyeing or in the same bath as dyeing. For example, when reduction soaping is carried out, it is preferable to carry out the functionalization treatment after dyeing and reduction soaping, from the viewpoint of preventing a compound having a specific functional group (e.g., a phenolic polymer compound) attached to the substrate from coming off during soaping.

[0226] The amount of the compound having a specific functional group attached to 100 parts by mass of the substrate after functionalization treatment is preferably 1.0 part by mass to 7.0 parts by mass, which is preferable from the viewpoint of achieving both high levels of durable water repellency and texture.

[0227] In the above method (2), an example of a substrate into which a specific functional group has been introduced is cationic dyeable polyester (CD-PET). From the viewpoint of good water repellency of the resulting textile product, the zeta potential of the surface of such a substrate is preferably −100 mV to −0.1 mV, or −50 mV to −1 mV. The zeta potential can be measured using a zeta potential / particle size measurement system (for example, model ELSZ-1000ZS, manufactured by Otsuka Electronics Co., Ltd.).

[0228] <Formation of Additional Layer> In addition to the substrate and the dispersion-derived component, the textile product may include an additional layer disposed on the substrate. In one embodiment, the woven / knitted fabric of the present disclosure may be provided as a laminated fabric having a breathable waterproof layer on one side thereof. The breathable waterproof layer may be laminated to the woven / knitted fabric directly or via an adhesive layer. When the laminated fabric is used for clothing applications, etc., it may be arranged so that the woven / knitted fabric side (i.e., the side opposite the breathable waterproof layer) is exposed to rainwater, etc. Such laminated fabrics have excellent water repellency and breathable waterproof properties, and the breathable waterproof layer does not peel off even in harsh environments, making them suitable for outdoor applications such as uniforms, sportswear, and outdoor products.

[0229] The moisture-permeable waterproof layer may be a layer of a resin having waterproof and moisture-permeable properties. The resin may be applied directly to the woven or knitted fabric, or may be laminated on one side of the woven or knitted fabric via an adhesive layer described below. For example, when a mixed fiber interlaced yarn having minute protrusions due to loops or slack is used in the woven or knitted fabric, the protrusions become firmly entangled with the adhesive layer or the moisture-permeable waterproof layer, thereby exerting an anchoring effect, making it even more difficult for the woven or knitted fabric and the moisture-permeable waterproof layer to peel off. In ordinary woven or knitted fabrics (woven or knitted fabrics in which the above-mentioned protrusions are not sufficiently maintained on the surface), the anchoring effect tends not to be exerted well, and the woven or knitted fabric and the moisture-permeable waterproof layer tend to peel off easily.

[0230] The main component of the resin constituting the moisture-permeable waterproof layer is preferably a polyurethane resin, and for example, the polyurethane resin is preferably contained in a proportion of 80% by mass or more. Polyurethane resins are generally suitable for forming resin layers that are moisture-permeable and waterproof. The polyurethane resin may be a reaction product of a polyisocyanate and a polyol, and conventionally known polyurethane resins can be used. The moisture-permeable waterproof layer may have, for example, a microporous structure or a non-porous structure. When the moisture-permeable waterproof layer has a microporous structure, inorganic fine powders can be contained in the moisture-permeable waterproof layer to ensure the desired moisture permeability. Examples of inorganic fine powders include fine powders of silicon dioxide, aluminum dioxide, titanium dioxide, etc. The average primary particle diameter of the inorganic fine powder is preferably about 7 to 40 nm. The content of the inorganic fine powder is preferably 3 to 50% by mass, and more preferably 5 to 50% by mass, of the total amount of the moisture-permeable waterproof layer.

[0231] The thickness of the moisture-permeable waterproof layer is preferably 5 μm or more, or 10 μm or more, and preferably 30 μm or less, from the viewpoints of the balance between waterproofness and moisture permeability, texture, and tear strength.

[0232] The laminated fabric may include an adhesive layer, and the woven or knitted fabric and the moisture-permeable waterproof layer may be laminated via the adhesive layer.

[0233] The adhesive constituting the adhesive layer is preferably one that has excellent compatibility with the moisture-permeable waterproof layer. For example, when the resin constituting the moisture-permeable waterproof layer is mainly composed of polyurethane resin, a preferred adhesive is a polyurethane-based adhesive. The polyurethane-based adhesive may be an ether-based, ester-based, polycarbonate-based, or the like, but is preferably an ether-based adhesive from the viewpoint of moisture permeability.

[0234] The adhesive layer may be formed over the entire surface of the woven or knitted fabric on the side on which the moisture-permeable waterproof layer is formed, or may be formed in a pattern from the viewpoints of moisture permeability, texture, etc. In either case, it is preferable that the adhesive layer be uniformly disposed over the entire surface.

[0235] The thickness of the adhesive layer is preferably 10 μm or more, or 20 μm or more, from the viewpoint of durability of the laminated fabric, and is preferably 100 μm or less, or 80 μm or less, from the viewpoint of production costs, because if the thickness of the adhesive layer exceeds 100 μm, further improvement in adhesiveness is poor even if the thickness is increased.

[0236] The laminated fabric may further have a lining fabric on the side of the moisture-permeable waterproof layer opposite the woven / knitted fabric side. When the lining fabric protects the moisture-permeable waterproof layer, waterproofness (water pressure resistance) and strength are further improved.

[0237] The laminated fabric can have excellent waterproof properties. In one embodiment of the laminated fabric, the water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method) is preferably 10,000 mm or more, or 15,000 mm or more, or 16,000 mm or more, or 20,000 mm or more. The upper limit of the water level is not particularly limited, but in one embodiment, it may be 50,000 mm or less, or 25,000 mm or less.

[0238] The laminated fabric may have excellent moisture permeability. In one embodiment, the moisture permeability measured in accordance with JIS L 1099:2012 B-1 method (potassium acetate method) is preferably 10,000 g / m 2 ・24 hours or more, or 15,000 g / m 2 ・24 hours or more, or 20,000 g / m 2 The upper limit of the moisture permeability is not particularly limited, but in one embodiment, it is 40,000 g / m 2 ・24 hours or less, or 35,000 g / m 2 - May be 24h·mm or less.

[0239] In the laminated fabric, delamination between the woven / knitted fabric and the moisture-permeable waterproof layer can be suppressed. In one embodiment of the laminated fabric, the peel strength between the woven / knitted fabric and the moisture-permeable waterproof layer, measured according to the method of JIS L 1089, may be, for example, 5 N / 2.54 cm or more, or 5 to 50 N / 2.54 cm, or 6 to 30 N / 2.54 cm, or 9 to 25 N / 2.54 cm. Methods for improving the peel strength include using a woven / knitted fabric that has not been subjected to calendering, and providing an adhesive layer.

[0240] Examples of methods for producing laminated fabrics include the following: "1" A method comprising the step of forming a moisture-permeable waterproof layer by applying a resin constituting the moisture-permeable waterproof layer to the surface of a woven or knitted fabric; and "2" A method comprising the step of forming an adhesive layer on the woven or knitted fabric or on the moisture-permeable waterproof layer, and bonding the woven or knitted fabric and the moisture-permeable waterproof layer via the adhesive layer. It is preferable to maintain as many protrusions on the fabric surface as possible in the woven or knitted fabric used in the laminated fabric. For example, if the woven or knitted fabric is subjected to a calendering process, the fine protrusions of the mixed fiber intertwined yarns may be crushed, resulting in a flat surface, making it impossible to achieve a specific water droplet rolling angle. Furthermore, calendering may not adequately maintain the air retention layer, making it impossible to achieve the desired water repellency. Therefore, it is preferable to carefully consider the calendering conditions. For example, it is sufficient to adopt conditions that do not excessively reduce the protrusions of the mixed fiber intertwined yarns (e.g., a temperature of 130°C or higher and a linear pressure of 200 to 20,000 N / cm). Calendering may also be performed without heating.

[0241] In the above method "1," the resin constituting the moisture-permeable waterproof layer can be applied to the surface of the woven or knitted fabric by, for example, a coating method. In the coating method, a knife coater or a comma coater can be used. From the viewpoint of obtaining excellent moisture permeability, it is preferable to obtain the moisture-permeable waterproof layer by a wet method.

[0242] In the method "2" above, an example of a technique for forming an adhesive layer on a woven or knitted fabric or a moisture-permeable waterproof layer is a lamination method. In the lamination method, a resin solution or a hot melt method can be used to form the adhesive layer. First, a moisture-permeable waterproof layer-forming resin composition (e.g., a resin composition containing a resin and an organic solvent) is applied to the surface of a release material (such as release paper, release cloth, or release film) while providing a clearance and adjusting the thickness, and then heat-treated to completely react and form a moisture-permeable waterproof layer (film). The release material may be removed as appropriate after the moisture-permeable waterproof layer is formed. Then, an adhesive layer is formed on the woven or knitted fabric or the moisture-permeable waterproof layer. For example, in a method using a resin solution, a two-component curing polyurethane resin solution with a viscosity adjusted to a range of 500 to 5,000 mPa·s may be applied entirely or in a pattern. The adhesive layer is then dried to form an adhesive layer, and the woven or knitted fabric and the moisture-permeable waterproof layer are bonded together via the adhesive layer and then pressed together (e.g., thermocompression). On the other hand, in the case of hot melt, it is preferable to use a moisture-curing resin that reacts with moisture in the air, and in practice, it is more preferable to use one that melts in a temperature range of about 80 to 150°C. In this case, the hot melt resin is first melted while taking into consideration the melting point of the resin and its viscosity when melted. The molten resin is then applied to the woven or knitted fabric or the moisture-permeable waterproof layer, and allowed to mature while cooling at room temperature to form an adhesive layer. The woven or knitted fabric and the moisture-permeable waterproof layer can then be bonded together via the adhesive layer and pressure-bonded.

[0243] After the moisture-permeable waterproof layer is formed, the lining fiber fabric may be laminated thereon by any conventionally known method, and the textile product of this embodiment is obtained in this manner.

[0244] The textile product of this embodiment is suitable for use in clothing (for example, uniforms, men's wear, women's wear, sportswear, etc.) and other applications.

[0245] The present invention will be further explained below with reference to examples, but the present invention is not limited to these examples in any way.

[0246] Examples 1 to 24, Comparative Examples 1 to 4 Synthesis of Organo-Modified Silicones Synthesis Example 1 Synthesis of Copolymer of Dimethylsiloxane and Methylhydrogensiloxane Methylhydrogensilicone was synthesized using hexamethyldisiloxane (available from Tokyo Chemical Industry Co., Ltd.), methylhydrogensilicone (available from Shin-Etsu Chemical Co., Ltd., Momentive Corporation, etc.), octamethylcyclotetrasiloxane (available from Tokyo Chemical Industry Co., Ltd.), and sulfuric acid. A three-neck flask was charged with methylhydrogensilicone (Si—H: 0.5 mol), sulfuric acid was added, and while flowing nitrogen gas, 0.44 mol of octamethylcyclotetrasiloxane Si—Me and 0.06 mol of hexamethyldisiloxane Si—Me were charged. The mixture was heated to 80°C and reacted for 7 hours, after which the mixture was distilled under reduced pressure until the total concentration of D4 / D5 / D6 siloxanes reached the predetermined concentration shown in Table 1. D4 is octamethylcyclotetrasiloxane, D5 is decamethylcyclopentasiloxane, and D6 is dodecamethylcyclohexasiloxane. The D4 / D5 / D6 siloxane concentrations were confirmed using a GC / MS (gas chromatograph mass spectrometer) (Agilent Technologies, Inc., model numbers 7697A, 7890A, and 5975C). As a result, the target copolymer of dimethylsiloxane and methylhydrogensiloxane (H silicone 3) was obtained. 1 Measurement using a H NMR (nuclear magnetic resonance apparatus) (manufactured by JEOL, model number ECZ500R) confirmed that the H silicone 3 had a SiH:SiCH molar ratio of 5:5.

[0247] (Addition Reaction) The H silicone 3 obtained above and a mixed solution of platinum (IV) chloride in ethylene glycol monobutyl ether and toluene as a hydrosilylation catalyst were charged into a flask so that the platinum concentration relative to the reactants in the system was 5 ppm. The atmosphere in the flask was replaced with nitrogen, and 1 equivalent of 1-octene was added dropwise to the mixture in the flask relative to 1 equivalent of the Si-H reactive group of the H silicone 3. The inside of the vessel was heated to 120°C, and the addition reaction was carried out for 6 hours. Completion of the addition reaction was confirmed by analyzing the obtained organo-modified silicone with an FT-IR (Fourier transform infrared spectrometer) (manufactured by Thermo Fisher Scientific, model number NICOLET is20) and confirming that the absorption spectrum derived from the SiH group of the H silicone 3 had disappeared. (In general formula (1), R 20 , R 21 , R 22 = CH3, R 23 =C8H 17 , a:b=5:5, R 30 ~R 35 =CH3) The amount of cyclic siloxane (γ) represented by general formula (1a) was confirmed by GC / MS. This confirmed that the cyclic siloxane (γ) in the organo-modified silicone was only D4 / D5 / D6 siloxane, so the total amount of D4 / D5 / D6 siloxane was considered to be the amount of cyclic siloxane (γ).

[0248] Synthesis Examples 2 to 17 Organo-modified silicones were synthesized in the same manner as in Synthesis Example 1, using the combinations of copolymers of dimethylsiloxane and methylhydrogensiloxane and α-olefins shown in Tables 1 and 2, with α-olefin being charged in an amount of 1 equivalent per equivalent of the reactive group SiH of each methylhydrogensilicone.

[0249] <Preparation of Organo-Modified Silicone Emulsion> 20 g of the organo-modified silicone obtained in the above Synthesis Example, 3 g of sorbitan fatty acid ester (available from Kao Corporation, HLB 7 or less), 4.5 g of polyoxyethylene alkyl ether (available from Daiichi Kogyo Co., Ltd., HLB 8 to 14), and 0.75 g of cationic emulsifier (Lipoguard T-28, available from Kao Corporation) were charged and mixed by heating until uniform. After becoming uniform, 71.75 g of water was charged and emulsified and dispersed with ultrasound for 10 minutes to obtain an organo-modified silicone emulsion (organo-modified silicone content: 20% by mass).

[0250] <Synthesis of Acrylic Polymer> <Acrylic Polymer 1> 30.0 g of stearyl acrylate, 0.2 g of Noigen XL-100 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7), 1.3 g of Noigen XL-60 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 12.5), 0.5 g of Noigen XL-40 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 10.5), 0.4 g of alkyl (C16-18) trimethylammonium chloride, 12.5 g of tripropylene glycol, and 54.8 g of water were placed in an autoclave and mixed and stirred at 45°C to form a mixed solution. This mixed solution was irradiated with ultrasound to emulsify and disperse all of the monomers. Next, 0.2 g of azobis(isobutylamidine) dihydrochloride and 0.08 g of dodecyl mercaptan were added to the mixed solution, and radical polymerization was carried out at 60°C for 6 hours under a nitrogen atmosphere, thereby obtaining an acrylic polymer emulsion (acrylic polymer 1) containing 30.0% by mass of an acrylic polymer.

[0251] <Acrylic Polymer 2> An autoclave was charged with 16.0 g of stearyl acrylate, 3.2 g of behenyl acrylate, 4.8 g of stearyl methacrylate, 0.2 g of Noigen XL-100 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7), 1.3 g of Noigen XL-60 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 12.5), 0.5 g of Noigen XL-40 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 10.5), 0.4 g of alkyl (C16-18) trimethylammonium chloride, 12.5 g of tripropylene glycol, and 54.8 g of water, and the mixture was stirred at 45°C to prepare a mixed solution. This mixed solution was irradiated with ultrasound to emulsify and disperse all of the monomers. Next, 0.2 g of azobis(isobutylamidine) dihydrochloride and 0.08 g of dodecyl mercaptan were added to the mixed solution, and radical polymerization was carried out at 60°C for 6 hours under a nitrogen atmosphere while continuously injecting 6.0 g of vinyl chloride into the autoclave so as to maintain the internal pressure of the autoclave at 0.3 MPa, thereby obtaining an acrylic polymer emulsion containing 30.0% by mass of an acrylic polymer (acrylic polymer 2).

[0252] <Acrylic Polymer 3> 19.2 g of stearyl acrylate, 4.2 g of stearyl methacrylate, 0.6 g of diacetone acrylamide, 0.2 g of Noigen XL-100 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7), 1.3 g of Noigen XL-60 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 12.5), 0.5 g of Noigen XL-40 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 10.5), 0.4 g of alkyl (C16-18) trimethylammonium chloride, 12.5 g of tripropylene glycol, and 54.8 g of water were placed in an autoclave and mixed and stirred at 45°C to form a mixed solution. This mixed solution was irradiated with ultrasound to emulsify and disperse all of the monomers. Next, 0.2 g of azobis(isobutylamidine) dihydrochloride and 0.08 g of dodecyl mercaptan were added to the mixed solution, and radical polymerization was carried out at 60°C for 6 hours under a nitrogen atmosphere while 6.0 g of vinylidene chloride was continuously injected into the autoclave so as to maintain the internal pressure of the autoclave at 0.3 MPa, thereby obtaining an acrylic polymer emulsion (acrylic polymer 3) (pH = 2.2) containing 30.0% by mass of the acrylic polymer.

[0253] <Acrylic Polymer 4> 22.5 g of stearyl acrylate, 0.75 g of LATEMUL PD-420, 0.75 g of LATEMUL PD-430, 0.2 g of Noigen XL-100 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7), 1.3 g of Noigen XL-60 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 12.5), 0.5 g of Noigen XL-40 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 10.5), 0.4 g of alkyl (C16-18) trimethylammonium chloride, 12.5 g of tripropylene glycol, and 54.8 g of water were placed in an autoclave and mixed and stirred at 45°C to obtain a mixed solution. This mixed solution was irradiated with ultrasound to emulsify and disperse all of the monomers. Next, 0.2 g of azobis(isobutylamidine) dihydrochloride and 0.08 g of dodecyl mercaptan were added to the mixed solution, and radical polymerization was carried out at 60°C for 6 hours under a nitrogen atmosphere, thereby obtaining an acrylic polymer emulsion (acrylic polymer 4) (pH = 2.1) containing 30.0% by mass of an acrylic polymer.

[0254] <Acrylic Polymer 5> 3.3 g of triethanolamine, 3.3 g of RHODAFAC ASI 80, and 3.3 g of water were dissolved to a homogeneous solution while cooling. This solution was mixed with 990.1 g of acrylic polymer 4 (pH = 2.1) to obtain an acrylic polymer emulsion (acrylic polymer 5) (pH = 3.5) containing 29.7 mass% of the acrylic polymer.

[0255] <Acrylic Polymer 6> 3.3 g of triethanolamine, 3.3 g of RHODAFAC ASI 80, and 3.3 g of water were dissolved to a homogeneous solution while cooling. This solution was mixed with 990.1 g of acrylic polymer 3 (pH = 2.2) to obtain an acrylic polymer emulsion (acrylic polymer 6) (pH = 3.5) containing 29.7 mass% of the acrylic polymer.

[0256] <Synthesis of Urethane Polymer> (Urethane Polymer Synthesis Example 1) 206.74 g of ditrimethylolpropane, 469.87 g of stearic acid, and 3.4 g of p-toluenesulfonic acid were placed in a 1000 ml flask and heated to 140°C under a nitrogen atmosphere. A dehydration reaction was then carried out at 140-190°C for 5 hours under a nitrogen stream at a heating rate of approximately 0.4°C / min. The nitrogen flow rate was 5 ml per minute. After completion of the reaction, the acid value of the synthesized product was measured. The acid value was 2.0 mgKOH / g.

[0257] Next, 101.12 g of the above reaction product was placed in a 300 ml flask, and 23.78 g of hexamethylene diisocyanate, 25 g of methyl ethyl ketone, and 0.125 g of a bismuth catalyst (Neostan U-600, manufactured by Nitto Kasei Co., Ltd.) were added, followed by a reaction at 80°C for 7 hours. The reaction was continued until the NCO% reached 0.64%. After the reaction, the temperature was lowered to 40°C, and then 2.36 g of 3,5-dimethylpyrazole was added and the reaction was continued at 40°C for 1 hour to obtain a urethane polymer. The weight-average molecular weight of the resulting urethane polymer was measured using gel permeation chromatography (HLC-8320 GPC (TOSOH CORPORATION)), and the weight-average molecular weight (Mw) was 11,700.

[0258] The obtained urethane polymer is a compound represented by the general formula (UI-1) in which R U31 is the residue obtained by removing four hydroxy groups from ditrimethylolpropane, d is 2, e is 2, W 1 is an ester group, R U32 is a heptadecyl group, V 1 is a hydroxy group, and a polyfunctional compound in which R U33 is a hexylene group and f is 2, and then the remaining unreacted isocyanate groups are blocked with 3,5-dimethylpyrazole.

[0259] Into a 500 mL stainless steel container, 120 g of the obtained urethane polymer, 50 g of methyl ethyl ketone, 5 g of Decaglin 1-L (nonionic surfactant, manufactured by Dai-ichi Kogyo Seiyaku), 5 g of Decaglin 1-SV (nonionic surfactant, manufactured by Dai-ichi Kogyo Seiyaku), and 5 g of Arcard T-28 (cationic surfactant, manufactured by Lion Specialty Chemicals) were placed and heated to 50 ° C. to dissolve. Next, 215 g of hot water at 80 ° C. was added, and the mixture was emulsified for 20 minutes while maintaining the temperature at 80 ° C. using an ultrasonic emulsifier US-600E (Nihon Seiki Seisakusho Co., Ltd.). The mixture was then cooled to obtain a urethane polymer emulsion containing 30.0% by mass of urethane polymer.

[0260] <Other Polymers> Zelan R3 (available from Chemours)

[0261] <Additional ingredients> Crosslinking agent NK Assist NY-11 (manufactured by Nicca Chemical Co., Ltd.)

[0262] <Preparation of Dispersion> Dispersions were obtained by mixing the components and water as the liquid medium at room temperature to obtain the compositions shown in Tables 4 and 5 (the blending amounts in the tables are based on mass %). That is, in the example shown in Table 4, an organo-modified silicone emulsion, a crosslinking agent, and water were mixed, and in the example shown in Table 5, an organo-modified silicone emulsion, a hydrophobic polymer emulsion, a crosslinking agent, and water were mixed.

[0263] Examples 25 to 29 Synthesis of Acrylic Polymer: Internal Polymerization In the presence of organo-modified silicone, monomer components, which are raw materials for the acrylic polymer, were polymerized.

[0264] <Acrylic Polymer 7> An emulsion (acrylic polymer 7) containing 27.5% by mass of an acrylic polymer and further containing 2.5% by mass of an organo-modified silicone was obtained in the same procedure as in the preparation of acrylic polymer 4, except that the organo-modified silicone of Synthesis Example 2 was also added during mixing and stirring at 45°C to obtain a mixed liquid in the preparation of acrylic polymer 4.

[0265] <Acrylic Polymer 8> An emulsion (acrylic polymer 8) containing 27.5% by mass of an acrylic polymer and further containing 2.5% by mass of an organo-modified silicone was obtained in the same manner as in the preparation of acrylic polymer 7, except that the organo-modified silicone of Synthesis Example 4 was used instead of that of Synthesis Example 2.

[0266] <Acrylic Polymer 9> An autoclave was charged with 12.8 g of stearyl acrylate, 2.6 g of stearyl methacrylate, 0.6 g of diacetone acrylamide, 0.2 g of Noigen XL-100 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=14.7), 1.3 g of Noigen XL-60 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5), 0.5 g of Noigen XL-40 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=10.5), 0.4 g of alkyl (C16-18) trimethylammonium chloride, 12.5 g of tripropylene glycol, and 54.8 g of water, and then 10 g of the organo-modified silicone of Synthesis Example 4 was added, and the mixture was mixed and stirred at 45°C to obtain a mixed solution. This mixture was irradiated with ultrasound to emulsify and disperse all of the monomers. Next, 0.2 g of azobis(isobutylamidine) dihydrochloride and 0.08 g of dodecyl mercaptan were added to the mixture, and radical polymerization was carried out at 60°C for 6 hours under a nitrogen atmosphere while continuously injecting 4.0 g of vinylidene chloride into the autoclave to maintain the internal pressure at 0.3 MPa, thereby obtaining an emulsion (acrylic polymer 9) containing 20.0 mass% of the acrylic polymer and also containing 10.0 mass% of the organo-modified silicone.

[0267] <Acrylic Polymer 10> An emulsion (acrylic polymer 10) containing 27.5% by mass of an acrylic polymer and further containing 2.5% by mass of an organo-modified silicone was obtained in the same procedure as for the preparation of acrylic polymer 7, except that the organo-modified silicone of Synthesis Example 16 was used instead of that of Synthesis Example 2.

[0268] <Additional ingredients> Crosslinking agent NK Assist NY-11 (manufactured by Nicca Chemical Co., Ltd.)

[0269] <Preparation of Dispersion> Each component and water as a liquid medium were mixed at room temperature so as to have the composition shown in Table 6 (the blending amounts in the table are based on mass %) to obtain a dispersion.

[0270] The cyclic siloxane concentration in the dispersion is calculated as follows: [Cyclic siloxane concentration (unit: ppm by mass)] = [Total amount of D4 / D5 / D6 per gram of organo-modified silicone (unit: g)] x [mass ratio of organo-modified silicone in organo-modified silicone emulsion] x [mass ratio of organo-modified silicone emulsion in dispersion] x 10 6

[0271] <Production of textile products> The following fabrics were used as treated fabrics: Polyester (PET) / polyurethane (PU) blend fabric (polyester / polyurethane mass ratio = 85 / 15) 100% polyester (PET) woven fabric 100% nylon (Ny) woven fabric 100% cotton woven fabric Polyester / cotton blend fabric (polyester / cotton = 70 / 30) White 100% polyester tricot knit

[0272] Each of the treated fabrics was immersed in 100 g of the dispersion liquid according to each Example and Comparative Example at normal pressure and 20±5° C. for 30 seconds, and then heat-treated at 150° C. for 2 minutes to obtain a textile product. The obtained textile product was subjected to the following evaluations.

[0273] <Evaluation of Textile Products> (Evaluation of Anti-wicking Properties) A ​​portion of a 2.5 cm wide x 10 cm long textile product (using a white 100% polyester tricot knit as the treated fabric) from the bottom end in the longitudinal direction to 1.0 cm was immersed in red-colored water (0.1% soln. of Alizaline Rubinol 3GA) and observed for 2 hours. After 2 hours, the maximum distance from the bottom end of the red portion of the textile product (i.e., the highest height) was measured. The smaller the value, the better the anti-wicking properties.

[0274] (Initial water repellency of textile products) A test was conducted on textile products in accordance with JIS L 1092 (2009) 7.2 Water repellency test (spray test) using shower water at a temperature of 20°C. The results were visually evaluated using the following grades. If the characteristics were slightly better, a "+" was given to the grade, and if the characteristics were slightly worse, a "-" was given to the grade. The results are shown in Tables 4 and 5. Water repellency: Condition 5: No wetting or water droplets on the surface 4: No wetting on the surface, but small water droplets are present 3: Wetting in the form of small individual water droplets is present on the surface 2: Wetting is present on half of the surface, and small individual wetting particles penetrate the fabric 1: Wetting is present on the entire surface

[0275] (Durable Water Repellency of Textile Products) After washing 20 times (L-20) according to method 103 of JIS L 0217 (1995), the water repellency of the textile products was evaluated in the same manner as in the initial water repellency evaluation.

[0276] (Processing stability: gum-up) 1000 g of a test solution was prepared by diluting with water having a hardness of 16 so that the solid content concentration of the dispersion would be 1.8% by mass, and placed in a tray whose temperature could be controlled at 40°C. A 20 cm wide and 80 cm long piece of fabric to be treated (100% polyester woven fabric) was looped around the mangle and placed in the mangle so that it could be treated continuously, and continuous treatment was carried out for 1 hour at a mangle pressure of 0.4 MPa. After 1 hour, the amount of solid matter adhering to the mangle was observed visually and by touch, and evaluated according to the following criteria. Excellent: No solid matter was precipitated at all. Good: Very little solid matter was precipitated. Fair: A small amount of solid matter was present. Poor: A large amount of solid matter was present.

[0277] (Peel Strength) (Peel strength of textile products against coating) Testing was carried out in accordance with JIS K 6404-5 (1999). A hot melt adhesive tape ("MELCO Tape" manufactured by Sun Chemical Industry Co., Ltd.) was thermally bonded to the textile product as a base fabric at 150°C for 1 minute using a thermocompression bonding device, and the peel strength between the base fabric and the seam tape was measured using an autograph (AG-IS manufactured by Shimadzu Corporation). The gripper was pulled at a moving speed of 100 mm / min, and the average value of the stress was taken as the peel strength [N / inch].

[0278] (Evaluation of Chalk Marks on Textile Products) The surface of a textile product was scratched with a fingernail and visually evaluated on the following 5-point scale. The results are shown in Tables 4 and 5. 5: Clear fingernail marks are observed 4: Fingernail marks are observed 3: Slight fingernail marks are observed 2: Almost no fingernail marks are observed 1: No fingernail marks at all

[0279] (Hue) For textile products, the color difference ΔE*ab was calculated from the L*a*b* values ​​measured by SCI measurement using a Minolta spectrophotometer CM-3700A, Spectra Magic NX CM-S100W, light source D65, field of view 10 degrees, UV 100%, and the hue value was determined. The smaller the color difference, the better. Color difference formula: ΔE * ab = [(Ln * -L0 * ) 2 + (an * -a0 * ) 2 +(bn * -b0 * ) 2 ] 1 / 2 L0 * , a0 * , b0 * = hue value of reference fabric Ln * , an * , bn * = hue value of each test fabric

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286] The dispersion of the present invention can be suitably applied to, for example, the production of textile products.

Claims

1. The following general formula (1): [In formula (1), R 20 , R 21 and R 22 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and R 23 represents a hydrocarbon group having 6 to 50 carbon atoms having an aromatic ring, or an alkyl group having 6 to 100 carbon atoms, and R 30 , R 31 , R 32 , R 33 , R 34 and R 35 each independently represent a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 6 to 50 carbon atoms having an aromatic ring, or an alkyl group having 6 to 100 carbon atoms, and a represents an integer of 0 or more, b represents an integer of 1 or more, (a + b) is 10 to 200, and when a is 2 or more, a plurality of R 20 and R 21 may be the same or different from each other, and when b is 2 or more, a plurality of R 22 and R 23 may be the same or different from each other.], a dispersion containing an organomodified silicone (α) represented by the formula: In the dispersion, the following general formula (1a): [In formula (1a), R 20 and R 21 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and a1 is an integer of 30 or less.], a dispersion in which the amount of the cyclic siloxane (γ) represented by the formula is 1000 mass ppm or less.

2. R in the general formula (1) 23 The dispersion according to claim 1, wherein R is a saturated hydrocarbon group having 6 to 50 carbon atoms.

3. The dispersion liquid according to claim 1, further comprising a hydrophobic polymer (β), wherein the hydrophobic polymer is at least one selected from the group consisting of a urethane-based polymer and an acrylic-based polymer.

4. The acrylic polymer has a structural unit derived from a monomer (A1) represented by the following general formula (A-1): [In formula (A-1), R 1 represents a hydrogen atom or a methyl group, and R 2 represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent.], The dispersion according to claim 3.

5. The dispersion liquid according to claim 3 or 4, wherein the acrylic-based polymer further comprises a structural unit derived from at least one monomer (VC) selected from the group consisting of vinyl chloride and vinylidene chloride.

6. The acrylic polymer is represented by the following general formula (A-2): [In formula (A-2), R 11 represents a hydrogen atom or a methyl group, R 12 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, Z represents an ester group or an amide group, and W represents -CO-R 13 (wherein R 13 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms), a -NH-CO-NH2 group, or the following formula (A-3): represents a group represented by.]. The dispersion liquid according to claim 3 or 4, further comprising a structural unit derived from the monomer (A-2) represented by 7. The acrylic polymer is (B1) a compound having an HLB of 7 to 18 and represented by the following general formula (I-1): [In formula (I-1), R 3 represents a hydrogen atom or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y 1 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.], (B2) a compound having an HLB of 7 to 18 and represented by the following general formula (II-1): [In formula (II-1), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group, and Y 2 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.], and (B3) a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having a hydroxyl group and a polymerizable unsaturated group, and further having a structural unit derived from at least one reactive activator (B) selected from the group consisting of: The dispersion according to claim 3 or 4.

8. The urethane polymer is at least the following general formula (UI-1): R U31 [-W 1 -R U32 d [-V 1 e (UI-1) [In formula (I-1), d represents an integer of 1 or more, e represents an integer of 2 or more, (d + e) is 3 to 6, and R U31 represents a (d + e)-valent organic group, W 1 represents a divalent group that is an ester group, an amide group, a urethane group, or a urea group, R U32 represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms, and V 1 represents a hydroxy group, an amino group, or a carboxy group. However, two or more of the e V 1 are a hydroxy group and / or an amino group.], a structural unit derived from a polyfunctional compound represented by the following general formula (UII): R U33 [-NCO] f (UII) [In formula (II), R U33 represents an f-valent organic group, and f represents an integer of 2 to 7.], and a hydrophobic compound containing a structural unit derived from an isocyanate compound represented by the formula, the dispersion liquid according to claim 3.​​ 9. A method for producing the dispersion liquid according to claim 3, comprising a mixing step of mixing an emulsion containing the organo-modified silicone (α) and the hydrophobic polymer (β).

10. A method for producing the dispersion liquid according to claim 3, comprising a polymerization step of polymerizing a monomer component which is a raw material of the hydrophobic polymer (β) in the presence of the organo-modified silicone (α) to obtain a dispersion liquid.

11. The method according to claim 10, wherein the polymerization step is carried out in the presence of an emulsion containing the organo-modified silicone (α).

12. A fiber product treated with the dispersion liquid according to claim 1.

13. A method for producing a fiber product, comprising a step of treating a substrate with the dispersion liquid according to claim 1.

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