Surface treatment agent composition, and water / oil-repellent fiber product and method for producing the same

Abstract

To provide a surface treatment agent composition comprising a silicone-based compound and capable of achieving both durable water repellency and resistance to peeling, and to provide a water / oil-repellent fiber product and a method for producing the same.SOLUTION: A surface treatment agent composition comprises: a silicone resin (A); and an organopolysiloxane (B) containing silanol groups, wherein the silicone resin (A) includes, as a component, at least one selected from MQ, MDQ, MTQ, and MDTQ {M, D, T, and Q respectively represent (R'')3SiO0.5 units, (R'')2SiO units, R''SiO1.5 units and SiO2 units, and R'' represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms}.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a surface treatment agent composition, a water- and oil-repellent textile product, and a method for producing the same. [Background technology]

[0002] Fluorine-based surface treatment agents having fluorine groups and textile products whose surfaces are imparted with water and oil repellency by treating the textile products with such fluorine-based surface treatment agents have been known. Such fluorine-based surface treatment agents are generally produced by homopolymerizing or copolymerizing a monomer having a fluoroalkyl group. Although textile products treated with fluorine-based surface treatment agents exhibit excellent water and oil repellency, the monomer having a fluoroalkyl group is difficult to decompose, which poses environmental problems.

[0003] Therefore, in recent years, research has been conducted into non-fluorine-based water repellents that do not contain fluorine. Patent Document 1 describes a water repellent agent containing at least one component selected from a urethane compound, an acrylic resin, and a reactive silicone, a silicone resin, and water. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-173185 Summary of the Invention [Problem to be solved by the invention]

[0005] Silicone compounds are useful as water- and oil-repellent components because they are non-fluorinated and have excellent water- and oil-repellent properties. The technology described in Patent Document 1 aims to provide a water repellent composition for fibers that exhibits low slippage when attached to textile products, etc., by using at least one component selected from a specific urethane compound, an acrylic resin, and a reactive silicone as the water-repellent component, a silicone resin, and water. However, conventional silicone-based water repellent compositions have a problem in that they lack sufficient peel resistance.

[0006] The present invention aims to solve the above-mentioned problems and to provide a surface treatment agent composition that uses a silicone compound and achieves both durable water repellency and peel resistance, as well as a water- and oil-repellent textile product and a method for producing the same. [Means for solving the problem]

[0007] This disclosure encompasses the following items: [1] The composition contains a silicone resin (A) and an organopolysiloxane (B) containing a silanol group, The silicone resin (A) is selected from the group consisting of MQ, MDQ, MTQ, and MDTQ {M, D, T, and Q are each (R'')3SiO 0.5 Unit, (R'')2SiO unit, R''SiO 1.5 units and SiO2 units, and R'' represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms. Surface treatment composition. [2] The silanol group-containing organopolysiloxane (B) is represented by the following formula (1): [ka] [In formula (1), X is an OH group or a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms which may have a substituent; n is a real number greater than or equal to 1, R is an OH group or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.] It has a structure represented by Item 2. The surface treatment agent composition according to item 1. [3] 3. The surface treatment composition according to item 1 or 2, further comprising an alkylpolysiloxane. [4] 4. The surface treatment agent composition according to any one of items 1 to 3, further comprising a polyfunctional isocyanate. [5] 5. The surface treatment agent composition according to any one of items 1 to 4, further comprising a hydrophobic organic solvent. [6] A water- and oil-repellent textile product obtained by treating the textile product with the surface treatment agent composition according to any one of items 1 to 5. [7] 6. A method for producing a water- and oil-repellent textile product, comprising a step of treating the textile product with a treatment liquid containing the surface treatment agent composition according to any one of items 1 to 5. [8] Item 3. A method for producing the surface treatment agent composition according to item 3, A method comprising mixing a silicone resin (A), an organopolysiloxane containing silanol groups (B), and an alkylpolysiloxane. [9] Item 5. A method for producing the surface treatment agent composition according to item 5, A method comprising mixing a silicone resin (A), an organopolysiloxane containing silanol groups (B), and a hydrophobic organic solvent. [Effects of the Invention]

[0008] According to one aspect of the present invention, it is possible to provide a surface treatment agent composition that uses a silicone compound and achieves both durable water repellency and peel resistance, as well as a water- and oil-repellent textile product and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0009] 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.

[0010] <Surface treatment agent composition> The surface treatment agent composition of this embodiment contains a silicone resin (A) and a silanol group-containing organopolysiloxane (B). The surface treatment agent composition of this embodiment can have excellent water and oil repellency and good peel resistance. Preferred examples of each component are described below.

[0011] <Silicone resin> In one embodiment, the silicone resin contains one or more components selected from MQ, MDQ, MT, MTQ, MDT, and MDTQ. The silicone resin is preferably solid at 25°C and is preferably an organopolysiloxane having a three-dimensional structure. The silicone resin preferably has a hardness of 20 or more, more preferably 60 or more, as measured with a Type A durometer in accordance with JIS K 6249:2003 13. Hardness Test. Here, M, D, T, and Q are each (R'')3SiO 0.5 Unit, (R'')2SiO unit, R''SiO 1.5 units and SiO2 units. In one embodiment, R'' is a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms.

[0012] In one embodiment, the silicone resins are commonly known as MQ resins, MT resins, or MDT resins, and may have moieties designated as MDQ, MTQ, or MDTQ.

[0013] The silicone resin can be obtained alone or as a solution obtained by dissolving the silicone resin in an alkyl polysiloxane and / or a suitable solvent other than the alkyl polysiloxane. Examples of the solvent other than the alkyl polysiloxane include n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, and mixtures of these solvents. The alkyl polysiloxane used as the solvent may constitute the alkyl polysiloxane described below that may be contained in the surface treatment agent composition of this embodiment.

[0014] Examples of solutions in which silicone resin is dissolved in alkylpolysiloxane include KF7312J (a 50:50 (mass ratio) mixture of trimethylsilyl group-containing polysiloxane:decamethylcyclopentasiloxane), KF7312F (a 50:50 (mass ratio) mixture of trimethylsilyl group-containing polysiloxane:octamethylcyclotetrasiloxane), KF9021L (a 50:50 (mass ratio) mixture of trimethylsilyl group-containing polysiloxane:low-viscosity methylpolysiloxane), and KF7312L (a 50:50 (mass ratio) mixture of trimethylsilyl group-containing polysiloxane:low-viscosity methylpolysiloxane) all of which are commercially available from Shin-Etsu Chemical Co., Ltd.

[0015] Examples of silicone resins that can be used alone include MQ-1600 solid resin (trimethylsilyl group-containing polysiloxane) and MQ-1640 flake resin (a mixture of trimethylsilyl group-containing polysiloxane and polypropylsilsesquioxane), both of which are commercially available from Dow Toray Co., Ltd. The above-mentioned commercially available products contain trimethylsilyl group-containing polysiloxane, and include MQ, MDQ, MT, MTQ, MDT, or MDTQ.

[0016] The silicone resin is preferably in the form of a solid with no melting point. The number average molecular weight of the silicone resin is preferably 100 or more, or 500 or more, or 1,000 or more from the viewpoint of the water and oil repellency of the surface treatment agent composition and product stability, and is preferably 1,000 or more, or 50,000 or less from the viewpoint of the water and oil repellency of the surface treatment agent composition. The weight-average molecular weight of the silicone resin is preferably 1,000 or more, or 2,000 or more, or 3,000 or more from the viewpoint of the water and oil repellency and product stability of the surface treatment agent composition, and is preferably 100,000 or less, or 80,000 or less, or 60,000 or less from the viewpoint of the processing stability of the surface treatment agent composition. The above molecular weights are values ​​measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a mobile phase and polystyrene as a standard substance.

[0017] <Silanol group-containing organopolysiloxane> Examples of organopolysiloxanes containing silanol groups (hereinafter referred to as silanol-modified silicones) include compounds containing silanol groups on the side chains and / or ends of organopolysiloxanes. The structure is not particularly limited as long as it contains a silanol group, but from the viewpoint of durable water repellency and peel resistance, it is preferable for the organopolysiloxane to have a silanol group at its terminal, and a silanol-modified silicone having the structure of formula (1) is particularly preferred. [ka] [In formula (1), X is an OH group or a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms which may have a substituent; n is a real number greater than or equal to 1, R is an OH group or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.] In the formula, multiple R's may be the same or different.

[0018] From the viewpoints of durable water repellency and peel resistance, X is preferably OH. When X is a hydrocarbon group having 1 to 40 carbon atoms, from the viewpoint of texture, it is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 16 carbon atoms, and even more preferably an alkyl group having 1 to 14 carbon atoms. Substituents for X include, but are not limited to, -O-, -S-, -CO-, -COO-, -NHCO-, -CONH-, -SO-, -S(=O)2-, -S(=O)2O-, and the like.

[0019] From the viewpoint of water repellency and texture, n is preferably a real number of 1 to 10,000, more preferably a real number of 1 to 8,000, and even more preferably a real number of 1 to 6,000.

[0020] From the viewpoints of water repellency and texture, R is preferably a hydrocarbon group having 1 to 32 carbon atoms, more preferably a hydrocarbon group having 1 to 28 carbon atoms, and even more preferably a hydrocarbon group having 1 to 24 carbon atoms. R may be an aliphatic group (open-chain or cyclic), an aromatic group, or a combination thereof, and is preferably an aliphatic group. Substituents for R include, but are not limited to, -O-, -S-, -CO-, -COO-, -NHCO-, -CONH-, -SO-, -S(=O)2-, -S(=O)2O-, and the like.

[0021] The functional group equivalent of the silanol-modified silicone, ie, the silanol group equivalent, is preferably 100 to 20,000 g / mol, more preferably 250 to 10,000 g / mol, and still more preferably 500 to 4,000 g / mol, from the viewpoints of initial water repellency, durable water repellency, and texture.

[0022] The silanol-modified silicone is preferably liquid at 25° C. The kinetic viscosity of the silanol-modified silicone at 25° C. is preferably 10 to 100,000 mm 2 / s is preferably 10 to 10,000 mm 2 / s is more preferable, and 10 to 5,000 mm 2More preferably, the kinematic viscosity at 25°C is 100,000 mm / s. 2 When the kinematic viscosity is 1 / s or less, workability tends to be easily ensured. The kinematic viscosity at 25°C means a value measured by the method described in JIS K 2283:2000 (Ubbelohde viscometer).

[0023] As the silanol-modified silicone, commercially available products can be used, such as X-21-5841 and KF-9701 (both of which are trade names of Shin-Etsu Chemical Co., Ltd.), XIAMETER TM PMX-0930, DOWSIL TM BY 16-879B, BY 16-892 (both are trade names manufactured by Dow-Toray Co., Ltd.), and the like.

[0024] The silanol-modified silicone may be used alone or in combination of two or more.

[0025] When the surface treatment agent composition of this embodiment is used as a treatment bath (for example, a treatment bath for treating fibers), the amount of silanol-modified silicone in the treatment bath can be 0.01 to 1 mass % based on the total amount of the surface treatment agent composition. Furthermore, during distribution, the amount of silanol-modified silicone in the treatment bath can be 0.1 to 50 mass %, or may be 0.2 to 20 mass %, based on the total amount of the surface treatment agent composition.

[0026] From the viewpoints of durable water repellency, peel strength, and seam slippage resistance, the blending amounts of the silicone resin and silanol-modified silicone may be 50 to 25,000 parts by mass, 100 to 10,000 parts by mass, 100 to 25,000 parts by mass, 500 to 25,000 parts by mass, or 900 to 25,000 parts by mass per 100 parts by mass of the silanol-modified silicone.

[0027] <Other ingredients> In one aspect, the surface treatment agent composition of the present embodiment may further contain a modified silicone other than the silanol-modified silicone. The modified silicone may be a polysiloxane having a reactive group at a side chain and / or at an end, and from the viewpoint of excellent abrasion resistance, a polysiloxane having a reactive group at a side chain and / or at both ends is preferred. The modified silicone is not particularly limited as long as it has a reactive group in the molecule, and examples thereof include epoxy-modified silicone, carboxy-modified silicone, and methylhydrogen silicone.

[0028] Epoxy-modified silicones include those having a structure in which an epoxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be an alkylene group, a divalent aromatic group, or a cycloaliphatic group. The alkylene group preferably has 1 to 10 carbon atoms. The divalent aromatic group preferably has 6 to 18 carbon atoms. The cycloaliphatic group is preferably a cycloaliphatic group having 4 to 12 carbon atoms. The epoxy group and the organic group are usually bonded in the form of a glycidyl ether. Examples of such functional groups include a 3-glycidoxypropyl group and a 2-glycidoxyethyl group. These functional groups may be present on the side chain or at the terminal of the polysiloxane.

[0029] Examples of carboxy-modified silicones include those having a structure in which a carboxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be an alkylene group or a divalent aromatic group. The alkylene group preferably has 2 to 18 carbon atoms. The divalent aromatic group preferably has 6 to 18 carbon atoms. Examples of such functional groups include a 3-carboxypropyl group and a 2-carboxyethyl group. These functional groups may be present on the side chain or at the terminal of the polysiloxane.

[0030] Methyl hydrogen silicone is a polydiorganosiloxane in which some of the side chains have been replaced with hydrogen atoms, with the hydrogen atoms directly bonded to silicon atoms. When using methyl hydrogen silicone, a catalyst may be used to improve reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine-based catalysts can be used. These catalysts are preferably organic acid metal salts, and fatty acids are preferred as organic acids. From the standpoint of safety, zinc stearate or the like can be used. It is preferable to use 1 to 40% by mass of the catalyst relative to the methyl hydrogen silicone, as this facilitates its effectiveness.

[0031] Since epoxy-modified silicone, carboxy-modified silicone, and methyl hydrogen silicone are all silicones having reactive groups, two or more of them may be mixed. Silicones having reactive groups preferably have film-forming properties. Film-forming properties refer to the formation of a solid film, not an oily or gel-like film, at 80°C to 200°C after the silicone is attached to the fiber surface in an emulsion state.

[0032] <Hydrophobic organic solvent> In one aspect, the surface treatment agent composition of the present embodiment may further contain a hydrophobic organic solvent, for which the amount of water required to dissolve 1 g of the organic solvent at 20°C is greater than 10 mL. In one aspect, 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 a hydrophobic organic solvent contributes to the formation of an emulsion dispersion in which the silicone resin is stably emulsified and dispersed, thereby contributing to the formation of a surface treatment agent composition with excellent product stability and processing stability. In the present disclosure, an emulsion dispersion (sometimes simply referred to as a dispersion) or emulsion dispersion refers to a liquid medium in which a liquid is present in an emulsified state and / or a solid is present in a dispersed state. In one aspect, an organic solvent, for which the amount of water required to dissolve 1 g of the organic solvent at 20°C is greater than 10 mL, is believed to contribute to improving water and oil repellency by improving the film-forming properties of the silicone compound, which is the water and oil repellent component, on fibers. The amount of water required to dissolve 1 g of the above organic solvent is a value measured in accordance with JIS K8001:2017 using the method described in the [Examples] section of this disclosure.

[0033] Without being bound by theory, it is speculated that when a silicone resin is emulsified and dispersed in a water-containing medium to form an emulsified dispersion or a surface treatment agent composition, the hydrophobic organic solvent of the present embodiment promotes O / W emulsified dispersion of the silicone resin, thereby contributing to improved emulsion dispersion stability of the silicone resin in the water-containing medium.

[0034] Organic solvents that require more than 10 mL of water to dissolve 1 g of the organic solvent at 20°C preferably have a structure consisting of carbon and hydrogen (i.e., a hydrocarbon structure) in the molecule, as this has a good effect of improving the emulsion dispersion stability of silicone resins. From this perspective, preferred hydrophobic 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, etc.), ethers (specific examples include dibutyl diglycol, diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethyl ether, etc.), and the like. The hydrophobic 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 hydrophobic organic solvents may be used alone or in combination of two or more.

[0035] The isoparaffin preferably has 4 or more carbon atoms, and more preferably 9 to 20 carbon atoms. Examples of such isoparaffins include IP Solvent IP-2028 (isoparaffin having 10 to 16 carbon atoms, manufactured by Idemitsu Kosan Co., Ltd.) and Macazol R (isododecane, manufactured by Maruzen Petrochemical Co., Ltd.).

[0036] As a mineral oil, the kinematic viscosity at 30°C is 50mm 2Examples of 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 by a method in accordance with JIS K 2283:2000. The paraffin may have a carbon number of, for example, 10 to 16. 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).

[0037] Mineral spirits with a boiling point of 130 to 230°C are particularly preferred.

[0038] In the surface treatment agent composition, the amount of organic solvent in which the amount of water required to dissolve 1 g of organic solvent at 20°C exceeds 10 mL is preferably 10 to 500 parts by mass, more preferably 20 to 400 parts by mass, and even more preferably 30 to 300 parts by mass, relative to 100 parts by mass of the silicone resin. The amount of the hydrophobic organic solvent is preferably within the above range in terms of the product stability over time and processing stability of the surface treatment agent composition.

[0039] <Emulsifier> In one embodiment, the surface treatment agent composition of the present embodiment may further include an emulsifier. In one embodiment, the emulsifier may be a surfactant. The surfactant may include one or more surfactants selected from cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants.

[0040] [Nonionic surfactants] Nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides.

[0041] The ethers include compounds having an oxyalkylene group (preferably a polyoxyethylene group). Esters include esters of alcohols and fatty acids. Examples of ester ethers include compounds in which an alkylene oxide, such as ethylene oxide, is added to an ester of an alcohol and a fatty acid. In the above ester or ester ether, the alcohol may be a monohydric to hexahydric, preferably dihydric to pentahydric, alcohol having 1 to 50 carbon atoms, preferably 3 to 30 carbon atoms. The alcohol is preferably an aliphatic alcohol. In the above ester or ester ether, the fatty acid may be a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, preferably 5 to 30 carbon atoms.

[0042] The alkanolamide may be formed from a fatty acid and an alkanolamine. The alkanolamide may be, for example, a monoalkanolamide or a dialkanolamide. The fatty acid may be a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, preferably 5 to 30 carbon atoms. The alkanolamine may be, for example, an alkanol having 2 to 50 carbon atoms, preferably 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0043] Examples of polyhydric alcohols include dihydric to pentahydric alcohols having 15 to 30 carbon atoms. The amine oxide may be an oxide of an amine. The amine may be a secondary amine or a tertiary amine. The number of carbon atoms in the amine oxide is preferably 5 to 50.

[0044] The nonionic surfactant preferably has an oxyalkylene group (preferably an oxyethylene group). The number of carbon atoms in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene units in the molecule of the nonionic surfactant is preferably 2 to 100.

[0045] More specific preferred examples of nonionic surfactants include alkylene oxide adducts of linear and / or branched, saturated and / or unsaturated aliphatic groups, polyalkylene glycol esters of linear and / or branched, saturated and / or unsaturated fatty acids, random or block copolymers of polyoxyethylene (POE) / polyoxypropylene (POP), alkylene oxide adducts of acetylene glycol, etc. The structures of the alkylene oxide adduct moiety and the polyalkylene glycol moiety are preferably polyoxyethylene (POE), polyoxypropylene (POP), or a random or block copolymer of POE / POP. From the viewpoint of environmental load, such as biodegradability and endocrine disrupting activity, the nonionic surfactant preferably does not contain an aromatic structure.

[0046] In a preferred embodiment, the nonionic surfactant is represented by the following formula (2): R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 (2) [In formula (2), R 1 represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group having 2 to 22 carbon atoms, R 2 When a plurality of groups are present, each group independently represents an alkylene group having 3 or more carbon atoms, R 3 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number greater than or equal to 2, and q is a number of 0 or 1 or more. It is a compound represented by the formula:

[0047] R 1 The number of carbon atoms in R is preferably 8 to 20, and more preferably 10 to 18. 1 is preferably a lauryl group, a tridecyl group, or an oleyl group. R 2is preferably an alkylene group having 3 to 10 carbon atoms, more preferably a propylene group or a butylene group. p is preferably 3 or more, or 5 or more, and is preferably 200 or less. q is preferably 2 or more, or 5 or more, and preferably 200 or less. In one embodiment, -(R 2 O) q - is a polyoxyalkylene chain.

[0048] The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether having a hydrophilic polyoxyethylene moiety and a hydrophobic oxyalkylene moiety (e.g., a polyoxyalkylene chain). Examples of the hydrophobic oxyalkylene moiety include an oxypropylene moiety and an oxybutylene moiety, with the oxypropylene moiety being preferred.

[0049] In a preferred embodiment, the nonionic surfactant is represented by the following formula (3): R 1 O-(CH2CH2O) p -H (3) [In formula (3), R 1 and p is as defined in formula (2). It is a compound represented by the formula:

[0050] In a preferred embodiment, the nonionic surfactant is a compound represented by the following formula group (4): C 10 H 21 O-(CH2CH2O) p -(C3H6O) q -H C 12 H 25 O-(CH2CH2O) p -(C3H6O) q -H C 15 H 31 O-(CH2CH2O) p -(C3H6O) q -H C 16 H 33 O-(CH2CH2O)p -(C3H6O) q -H C 17 H 35 O-(CH2CH2O) p -(C3H6O) q -H C 18 H 37 O-(CH2CH2O) p -(C3H6O) q -H C 12 H 25 O-(CH2CH2O) p -(C3H6O) q -C 12 H 25 C 15 H 31 O-(CH2CH2O) p -(C3H6O) q -C 15 H 31 C 16 H 33 O-(CH2CH2O) p -(C3H6O) q -C 12 H 25 iso-C 13 H 27 O-(CH2CH2O) p -(C3H6O) q -H C 10 H 21 COO-(CH2CH2O) p -(C3H6O) q -H C 16 H 33 COO-(CH2CH2O) p -(C3H6O) q -C 12 H 25 (4) [In the formula group (4), p and q are the same as defined in formula (2)] It is a compound represented by any one of the following:

[0051] More specific examples of nonionic surfactants include condensation products of ethylene oxide with hexylphenol, isooctamethylphenol, hexadecanol, oleic acid, alkane (C12-C16) thiols, sorbitan monofatty acids (C7-C19), or alkyl (C12-C18) amines.

[0052] When the nonionic surfactant has a polyoxyethylene block, the mass ratio of the polyoxyethylene block in the molecule may be, in one embodiment, 5 to 80 mass %, or 30 to 75 mass %, or 40 to 70 mass %.

[0053] The nonionic surfactant may be a single type or a combination of two or more types, but is preferably a combination of two or more types. In the combination of two or more types, at least one nonionic surfactant is represented by the R 1 Groups and / or R 3 Preferably, the alkyl group in the formula (4) is a branched alkyl group, such as an isotridecyl group (hereinafter referred to as a branched compound). The amount of the branched compound is preferably 5 to 100 mass%, or 8 to 50 mass%, or 10 to 40 mass%, relative to 100 mass% of the total of two or more nonionic surfactants. In a combination of two or more nonionic surfactants, at least one nonionic surfactant may be a compound other than the branched compound. Examples of such compounds include compounds represented by R in the formula (2) or (3) above. 1 Groups and / or R 3 or a compound in which the alkyl group in the above formula (4) is a saturated or unsaturated straight-chain alkyl group, such as a lauryl group.

[0054] Particularly preferred examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkylolamides, alkylalkanolamides, acetylene alcohols (e.g., acetylene glycol), oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, etc. From the viewpoint of reducing the dynamic surface tension of the surface treatment agent composition and thereby facilitating penetration of the composition into textile products, acetylene alcohols (e.g., acetylene glycol) or oxyethylene adducts of the acetylene alcohols are preferred as nonionic surfactants.

[0055] In a preferred embodiment, the nonionic surfactant is an alcohol having an unsaturated triple bond, or an alkylene oxide adduct of the alcohol (hereinafter, these are collectively referred to as a triple bond alcohol compound). The triple bond alcohol compound contains one or more triple bonds and one or more hydroxyl groups. The alcohol may be a monool or a polyol. The alkylene oxide adduct preferably includes a polyoxyalkylene adduct, such as a polyoxyethylene adduct, a polyoxypropylene adduct, or a random or block adduct of polyoxyethylene and polyoxypropylene.

[0056] The triple bond alcohol compound is represented by the following formula (5a) or (5b): HO-CR 11 R 12 -C≡C-CR 13 R 14 -OH (5a) [In formula (5a), R 11 , R 12 , R13 , and R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.] HO-CR 15 R 16 -C≡CH (5b) [In formula (5b), R 15 and R 16 each independently represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.] or an alkylene oxide adduct thereof. The alkylene oxide preferably has 1 to 20 carbon atoms, or 2 to 5 carbon atoms, and suitable examples of the alkylene oxide are ethylene oxide or propylene oxide. The number of added alkylene oxides is preferably 1 to 50. The alkyl group in the above formula (5a) or (5b) is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, or 1 to 6 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, butyl group, or isobutyl group.

[0057] Specific examples of triple bond alcohol compounds include acetylene diol, propargyl alcohol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3-hexyne-2,5-diol, 2-butyne-1,4-diol, and the like, as well as polyethoxylates and ethylene oxide adducts thereof.

[0058] The nonionic surfactant may be one or both of a compound having a triple bond and a compound not having a triple bond. In a combination of a compound having a triple bond and a compound not having a triple bond, the mass ratio of the compound having a triple bond (e.g., an acetylene alcohol compound) to the compound not having a triple bond (e.g., a nonionic surfactant having an oxyalkylene group) may be 10:90 to 90:10, or 20:80 to 80:20, in one embodiment.

[0059] In one aspect, the number average molecular weight of the nonionic surfactant may be 300 to 5,000, or 500 to 3,000. The number average molecular weight is a value measured using gel permeation chromatography (GPC) with a polyethylene glycol standard.

[0060] [Cationic surfactants] Examples of cationic surfactants include amines, amine salts, quaternary ammonium salts, imidazolines, and imidazolinium salts. In one embodiment, the cationic surfactant does not have an amide group. Suitable examples of the cationic surfactant are amine salts, quaternary ammonium salts, and oxyethylene adduct ammonium salts. Specific examples of the cationic surfactant include amine salt surfactants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, and quaternary ammonium salt surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride.

[0061] In a preferred embodiment, the cationic surfactant is represented by the following formula (6): R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - (6) [In formula (6), R 21 , R 22 , R 23 and R 24 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms, X represents an anionic group. The hydrocarbon group in formula (6) may have an oxygen atom, and may be, for example, an oxyalkylene group such as a polyoxyalkylene group. The number of carbon atoms in the alkylene moiety is, for example, 2 to 5. R 21 , R 22 , R23 or R 24 The hydrocarbon group as R may be an aliphatic, aromatic or combination thereof. 21 , R 22 , R 23 and R 24 are each independently preferably a hydrocarbon group having 1 to 30 carbon atoms.

[0062] R 21 , R 22 , R 23 and R 24 Specific examples of the group include alkyl groups (for example, methyl, butyl, stearyl, and palmityl groups), aryl groups (for example, phenyl groups), and aralkyl groups (for example, benzyl and phenethyl groups). Specific examples of X include halogens and acids. The halogens may be, for example, chlorine. The acids may be inorganic acids such as hydrochloric acid, or organic acids (particularly fatty acids) such as acetic acid. In a preferred embodiment, the cationic surfactant is a monoalkyltrimethylammonium salt. The number of carbon atoms in the alkyl moiety may be, for example, 4 to 30.

[0063] In a preferred embodiment, the cationic surfactant is an ammonium salt, particularly a quaternary ammonium salt. The cationic surfactant is represented by the following formula (7): R 31 p -N + R 32 q X - (7) [In formula (7), R 31 When a plurality of groups are present, each group independently represents a linear or branched, saturated or unsaturated aliphatic group having 12 or more carbon atoms, R 32 When a plurality of groups are present, each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a benzyl group, or a polyoxyethylene group, X represents a halogen atom or a fatty acid base having 1 to 4 carbon atoms; p is 1 or 2; q is 2 or 3, provided that p+q=4. The ammonium salt may be represented by the formula: R 31 The number of carbon atoms is preferably 12 to 50, or 12 to 30. R 32 In the polyoxyethylene group as the repeating number of oxyethylene units, in one aspect, the repeating number of oxyethylene units may be 1 to 50, or 2 to 50, or 3 to 50, and is preferably 1 or 2. X is preferably chlorine or bromine.

[0064] Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, and benzyldodecyldi(hydropolyoxyethylene)ammonium chloride.

[0065] [Anionic surfactants] Examples of anionic surfactants include fatty acids (salts) such as oleic acid, palmitic acid, sodium oleate, potassium palmitate, and triethanolamine oleate; hydroxyl group-containing carboxylic acids (salts) such as hydroxyacetic acid, potassium hydroxyacetate, lactic acid, and potassium lactate; polyoxyalkylene alkyl ether acetic acids (salts) such as polyoxyethylene tridecyl ether acetic acid (sodium salt); salts of carboxyl group-polysubstituted aromatic compounds such as potassium trimellitate and potassium pyromellitate; alkylbenzene sulfonic acids (salts) such as dodecylbenzene sulfonic acid (sodium salt); polyoxyalkylene alkyl ether sulfonic acids (salts) such as polyoxyethylene 2-ethylhexyl ether sulfonic acid (potassium salt); higher fatty acid amide sulfones such as stearoyl methyl taurine (sodium), lauroyl methyl taurine (sodium), myristoyl methyl taurine (sodium), and palmitoyl methyl taurine (sodium). alkylphosphonic acids (salts) such as octylphosphonate (potassium salt); aromatic phosphonic acids (salts) such as phenylphosphonate (potassium salt); alkylphosphonic acid alkyl phosphate esters (salts) such as 2-ethylhexylphosphonate mono 2-ethylhexyl ester (potassium salt); nitrogen-containing alkylphosphonic acids (salts) such as aminoethylphosphonic acid (diethanolamine salt); alkyl sulfate esters (salts) such as 2-ethylhexyl sulfate (sodium salt); polyoxyalkylene sulfate esters (salts) such as polyoxyethylene 2-ethylhexyl ether sulfate (sodium salt); long-chain sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate and sodium dioctyl sulfosuccinate, and long-chain N-acyl glutamates such as sodium N-lauroyl glutamate and disodium N-stearoyl-L-glutamate;

[0066] [Amphoteric surfactants] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0067] In one embodiment, the surfactant may be a combination of one or more nonionic surfactants, one or more ionic surfactants, and one or more amphoteric surfactants.

[0068] In one embodiment, the amount of the ionic surfactant is preferably 15% by mass or more, more preferably 20% by mass or more, and particularly preferably 25% by mass or more, based on 100% by mass of the total amount of surfactants. When a combination of a nonionic surfactant and an ionic surfactant is used, the mass ratio of the nonionic surfactant to the ionic surfactant is preferably 85:15 to 20:80, more preferably 80:20 to 40:60.

[0069] The amount of the ionic surfactant may be 0.05 to 10 parts by mass, for example, 0.1 to 8 parts by mass, relative to 100 parts by mass of the silicone resin.

[0070] The total amount of emulsifiers, particularly surfactants, may be 0.1 to 20 parts by mass, for example 0.2 to 10 parts by mass, relative to 100 parts by mass of the silicone resin.

[0071] The HLB of the surfactant is preferably 6 to 15, or 6.5 to 14, or 7 to 13, or 8 to 12, from the viewpoint of product stability of the surface treatment agent composition.

[0072] Throughout this disclosure, "HLB" refers to the Griffin HLB calculation. Here, the hydrophilic group refers to an ethylene oxide group. HLB=(hydrophilic group×20) / molecular weight HLB of nonionic surfactant = (molecular weight of hydrophilic group of nonionic surfactant) x 20 / molecular weight of nonionic surfactant

[0073] <Aqueous medium> The surface treatment agent composition of this embodiment may further contain an aqueous medium different from the hydrophobic organic solvent of this embodiment (i.e., an organic solvent for which the amount of water required to dissolve 1 g of the organic solvent at 20°C exceeds 10 mL). In one aspect, the aqueous medium is 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 method described in the [Examples] section of this disclosure. In one aspect, the aqueous medium is an alcohol. One type of alcohol may be used alone, or two or more types may be used in combination. The alcohol is not particularly limited, but examples include alcohols having 1 to 6 carbon atoms, and preferred examples include methanol, ethanol, isopropanol, glycerin, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, glycerin, butyl glycol, butyl diglycol, and sorbite. Other examples include compounds other than alcohols, such as N-methylpyrrolidone, dimethylformamide, and dimethyl sulfoxide. These organic solvents are miscible with water and may be contained in the surface treatment agent composition as a mixed solvent with water.

[0074] <Alkylpolysiloxane> The surface treatment agent composition of this embodiment contains an alkylpolysiloxane as a surface treatment component. In one aspect, the alkylpolysiloxane of this embodiment has a kinematic viscosity of 2 mm at 25°C. 2 The alkylpolysiloxane that can be contained in the surface treatment agent composition as a solvent (e.g., a solvent for a silicone resin) has a kinematic viscosity of 2 mm at 25°C. 2 / s or less.

[0075] The alkylpolysiloxane of this embodiment is nonvolatile. Whether an alkylpolysiloxane is nonvolatile or volatile can be determined as follows. A nonvolatile alkyl polysiloxane is one in which, when 1 g of the alkyl polysiloxane is spread on a 48 mm diameter glass petri dish and left at 25°C and normal pressure for 24 hours, the mass loss rate is 1% or less, and the alkyl polysiloxane is liquid or has plasticity at room temperature (25°C). Having plasticity means that the plasticity can be measured in accordance with JIS K 6249, where the plasticity is the value (unit: mm) when a load of 1 kgf is applied to a 4.2 g spherical sample at 25°C for 3 minutes. Furthermore, linear or cyclic alkyl polysiloxanes with a siloxane polymerization degree of 10 or more exhibit nonvolatility. On the other hand, linear or cyclic alkyl polysiloxanes with a siloxane polymerization degree of less than 10, particularly 7 or less, exhibit volatility at room temperature, and are therefore preferably used as part of a solvent rather than as the alkyl polysiloxane used as a surface treatment component of this embodiment. In one aspect, volatile silicones having a siloxane degree of polymerization of less than 10 are expressly excluded from the scope of alkylpolysiloxanes as surface treatment components of the present embodiments.

[0076] In one embodiment, the alkyl polysiloxane used as the surface treatment component is a compound in which the side chain and terminal of a chain organo polysiloxane are saturated hydrocarbon groups, or a compound in which the side chain of a cyclic organo polysiloxane is saturated hydrocarbon groups. Examples of such alkyl polysiloxanes include those represented by the following general formula (8):

[0077] [ka] [In formula (8), R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 each independently represents a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and v represents a number that makes the compound represented by formula (8) nonvolatile. and a compound represented by the following general formula (9):

[0078] [ka] [In formula (9), R 19 and R 20 each independently represents a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and w represents a number that makes the compound represented by formula (9) nonvolatile. Examples of the compound include compounds represented by the following formula:

[0079] In the compound represented by the general formula (8) used in this embodiment, R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 are each independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms. The number of carbon atoms in this saturated hydrocarbon group is preferably 1 to 10, from the viewpoints of facilitating the dissolution of silicone resin in the compound represented by general formula (8) and facilitating the acquisition of said compound. The saturated hydrocarbon group may be linear or branched. The saturated hydrocarbon group is preferably linear, and more preferably a linear alkyl group. The saturated hydrocarbon group is preferably a methyl group or an ethyl group, and more preferably a methyl group. v is a value that indicates that the compound represented by general formula (8) is nonvolatile and has a kinematic viscosity of 2 mm 2 / s, for example, can be appropriately selected so that it is within the range of the kinematic viscosity described below. From the viewpoint of making the alkylpolysiloxane non-volatile, v is preferably 3 or more, or 5 or more. Note that a compound in formula (8) where v is a number that makes the compound represented by formula (8) volatile can be used as a solvent for silicone resin, etc. Use of a volatile polysiloxane may improve the stability of the system. However, such a volatile alkylpolysiloxane is not used to define the parts by mass, mass ratio, etc. of the alkylpolysiloxane as the surface treatment component in this embodiment.

[0080] Examples of the compound represented by the general formula (8) include nonvolatile dimethylpolysiloxane and diethylpolysiloxane.

[0081] In the compound represented by the general formula (9) used in this embodiment, R 19 and R 20 are each independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms. The number of carbon atoms in this saturated hydrocarbon group is preferably 1 to 10. When the number of carbon atoms in the saturated hydrocarbon group is within the above range, silicone resins tend to dissolve easily in the compound represented by general formula (9), and the compound tends to be easily available. The saturated hydrocarbon group may be linear or branched. The saturated hydrocarbon group is preferably linear, and a linear alkyl group is more preferred. The saturated hydrocarbon group is preferably a methyl group or an ethyl group, and a methyl group is more preferred. w is a number that renders the compound represented by general formula (9) nonvolatile. w is preferably in the range of 10 to 1,000, or in the range of 20 to 1,000. Alkyl polysiloxanes in which w is a number that renders the compound represented by general formula (9) volatile, such as low-polymerization, volatile alkyl polysiloxanes in which w is in the range of 2 to 10, particularly 4 or 5, can be used as solvents for silicone resins. Such cyclic and volatile alkylpolysiloxanes tend to be easy to obtain and dissolve silicone resins, and can be suitably used in this embodiment.

[0082] w is the number at which the compound represented by general formula (9) becomes volatile, and examples of compounds suitable as solvents for silicone resins include decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane. However, as mentioned above, these are not used to define the mass ratio, etc., of the "alkylpolysiloxane" in this embodiment.

[0083] The alkylpolysiloxanes may be used alone or in combination of two or more.

[0084] The alkylpolysiloxane of this embodiment is preferably liquid at 25° C. The kinematic viscosity of the alkylpolysiloxane at 25° C. is 2 mm 2 / s super 100,000mm 2 / s or less is preferable, and 5 mm 2 / s or more 10,000mm 2 / s or less is more preferable, and 10 mm 2 / s or more 1,000mm 2 / s or less is more preferable, and 10 mm 2 / s or more 500mm 2 / s or less, and even more preferably 10 mm 2 / s or more 100mm 2 / s or less is particularly preferred. When the kinematic viscosity at 25°C is within the above range, the silicone resin tends to dissolve easily in the alkylpolysiloxane, and workability tends to be easily ensured. In this disclosure, the kinematic viscosity at 25°C refers to the value measured using the method described in JIS K 2283:2000 (Ubbelohde viscometer). Dynamic viscosity is 2mm 2 Although alkyl polysiloxanes of 0.1 to 1.0 wt. / s or less are not used in defining the mass ratio, etc., of the alkyl polysiloxane of this embodiment, they can be used as a solvent for the silicone resin in the system, etc. By using a volatile cyclic or chain alkyl polysiloxane in combination, it may be possible to improve the handling and workability of the silicone resin, etc., and the stability of the system.

[0085] In the surface treatment agent composition of this embodiment, the mass ratio of silicone resin to alkylpolysiloxane (silicone resin:alkylpolysiloxane) is preferably 10:90 to 90:10, or 20:80 to 70:30, or 30:70 to 60:40, from the viewpoints of water repellency and texture.

[0086] <Multifunctional isocyanate> In one embodiment, the surface treatment agent composition may further contain a polyfunctional isocyanate as a crosslinking component. The polyfunctional isocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule, and known polyisocyanate compounds can be used. Examples of polyfunctional isocyanates include diisocyanate compounds such as alkylene diisocyanates, aryl diisocyanates, and cycloalkyl diisocyanates, as well as modified polyisocyanate compounds such as dimers, trimers, or tetramers of these diisocyanate compounds. The alkylene diisocyanate preferably has 1 to 12 carbon atoms, the aryl diisocyanate preferably has 6 to 24 carbon atoms, and the cycloalkyl diisocyanate preferably has 3 to 24 carbon atoms. From the viewpoint of peel resistance, aliphatic isocyanates and alicyclic isocyanates are preferred.

[0087] Examples of diisocyanate compounds include 2,4 or 2,6-tolylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, phenylene diisocyanate, tolylene or naphthylene diisocyanate, 4,4'-methylene-bis(phenylisocyanate), 2,4'-methylene-bis(phenylisocyanate), 3,4'-methylene-bis(phenylisocyanate), 4,4'-ethylene-bis(phenylisocyanate), ω,ω'-diisocyanate-1,3-dimethylbenzylisocyanate, methyl ... benzene, ω,ω'-diisocyanato-1,4-dimethylcyclohexane, ω,ω'-diisocyanato-1,4-dimethylbenzene, ω,ω'-diisocyanato-1,3-dimethylcyclohexane, 1-methyl-2,4-diisocyanatocyclohexane, 4,4'-methylene-bis(cyclohexyl isocyanate), 3-isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate, acid-diisocyanate dimer, ω,ω'-diisocyanatodiethylbenzene, ω,ω'-diisocyanatodimethyltoluene, ω,ω'-diisocyanatodiethyltoluene, fumaric acid bis(2-isocyanatoethyl)ester, 1,4-bis(2-isocyanato-prop-2-yl)benzene, and 1,3-bis(2-isocyanato-prop-2-yl)benzene.

[0088] Examples of triisocyanate compounds include triphenylmethane triisocyanate, tris(isocyanatophenyl)-thiophosphate, etc. Examples of tetraisocyanate compounds include dimethyltriphenylmethane tetraisocyanate, etc.

[0089] The modified polyisocyanate compound derived from a diisocyanate compound is not particularly limited as long as it has two or more isocyanate groups, and examples thereof include polyisocyanates having a biuret structure, an isocyanurate structure, a urethane structure, a uretdione structure, an allophanate structure, a trimer structure, etc., and an adduct of an aliphatic isocyanate of trimethylolpropane. Polymeric MDI (MDI = diphenylmethane diisocyanate) can also be used as the polyisocyanate compound. The polyisocyanate compound can be used alone or in combination of two or more.

[0090] The isocyanate group of the polyfunctional isocyanate may be in its original form or may be a blocked isocyanate group blocked with a blocking agent. 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; phenols such as phenol, methylphenol, chlorophenol, isobutylphenol, tert-butylphenol, isoamylphenol, octylphenol, and nonylphenol; lactams such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam; active methylene compounds such as malonic acid dimethyl ester, malonic acid diethyl ester, acetylacetone, methyl acetoacetate, and ethyl acetoacetate; oximes such as formaldoxime, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; imidazole compounds such as imidazole and 2-methylimidazole; and sodium bisulfite. Among these, pyrazoles and oximes are preferred from the viewpoint of durable water repellency.

[0091] The polyfunctional isocyanate may be a water-dispersible isocyanate, which is a polyisocyanate that has been given water dispersibility by introducing a hydrophilic group into the polyisocyanate structure to impart a surfactant effect. Furthermore, a known catalyst such as an organotin or organozinc may be used in combination to promote the reaction between the silanol group and the isocyanate group.

[0092] From the viewpoints of water repellency, durable water repellency, and texture, the blending amount of the polyfunctional isocyanate in the surface treatment agent composition of the present embodiment is preferably 1 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of the silanol-modified silicone.

[0093] <Additional water-repellent ingredients> The surface treatment agent composition of the present embodiment may further contain, as an additional water-repellent component, for example, one or more of known fluorine-based polymers; hydrocarbon group-containing compounds such as aliphatic hydrocarbons, aliphatic carboxylic acids and their esters, polyolefins, and poly(meth)acrylic acid esters; and the like.

[0094] An example of a conventional fluorine-based polymer is NK Guard S-33 (manufactured by Nicca Chemical Co., Ltd.).

[0095] Examples of aliphatic hydrocarbons include paraffinic hydrocarbons, olefinic hydrocarbons, etc. The number of carbon atoms of the aliphatic hydrocarbons is preferably 12 or more.

[0096] The aliphatic carboxylic acid may be either saturated or unsaturated, and preferably has a carbon number of at least 12. Esterification products of such aliphatic carboxylic acids may also be used.

[0097] Examples of polyolefins include polyethylene, polypropylene, and ethylene-propylene copolymers.

[0098] The poly(meth)acrylic acid ester preferably has a hydrocarbon group having 12 or more carbon atoms connected via an ester bond. The hydrocarbon group preferably has 24 or less carbon atoms. The hydrocarbon group may be linear or branched, saturated or unsaturated, and may have an alicyclic or aromatic ring. Among these, linear groups are preferred, and linear alkyl groups are more preferred. The proportion of acrylic acid ester or methacrylic acid ester monomer in the polymer is preferably 80 to 100% by mass relative to the total amount of monomer units constituting the polymer. The weight-average molecular weight of the polymer, measured by gel permeation chromatography, is preferably 30,000 or more in terms of standard polystyrene. A copolymer of acrylic acid ester and methacrylic acid ester may also be used.

[0099] Examples of such poly(meth)acrylic acid esters (non-fluorinated polymers) include non-fluorinated acrylic polymers containing structural units derived from a (meth)acrylic acid ester monomer (A) (hereinafter also referred to as "component (A)") represented by the following general formula (A-1):

[0100] [ka]

[0101] [In formula (A-1), R 1 represents hydrogen, a methyl group, or a halogen group, and R 2 represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent.

[0102] The (meth)acrylic acid ester monomer (A) used in this embodiment and represented by the general formula (A-1) 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. Among these, linear groups are preferred, and linear alkyl groups are more preferred. In this case, the water repellency is improved. When the monovalent hydrocarbon group having 12 or more carbon atoms has a substituent, the substituent may be one or more of a hydroxy group, an amino group, a carboxy 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), R 2 is preferably an unsubstituted hydrocarbon group.

[0103] The number of carbon atoms in the hydrocarbon group is preferably 12 to 40. When the number of carbon atoms is 12 or more, water repellency is more likely to be improved when a surface treatment agent composition containing a non-fluorinated acrylic polymer is applied to a textile product or the like. On the other hand, when the number of carbon atoms is 40 or less, the texture of the textile product tends to be more improved when a surface treatment agent composition containing a non-fluorinated acrylic polymer is applied to a textile product or the like.

[0104] The number of carbon atoms in the hydrocarbon group is more preferably 12 to 24. When the number of carbon atoms is within this range, the water repellency and texture become particularly excellent. A particularly preferred hydrocarbon group is a linear alkyl group having 12 to 22 carbon atoms.

[0105] Examples of the component (A) include stearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, behenyl (meth)acrylate, ceryl (meth)acrylate, and melissyl (meth)acrylate.

[0106] The (A) component may have at least one functional group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an epoxy group, and an isocyanate group that can react with a crosslinking agent. 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. Furthermore, when the (A) component has an amino group, the texture of the resulting textile product can be further improved.

[0107] The component (A) is preferably a monofunctional (meth)acrylic acid ester monomer having one polymerizable unsaturated group in one molecule.

[0108] The component (A) may be used alone or in combination of two or more.

[0109] From the viewpoint of durable water repellency of the resulting textile product, the component (A) may be a combination of the acrylic acid ester monomer (a1) and the methacrylic acid ester monomer (a2).

[0110] The total constituent ratio of the monomers of the component (A) in the non-fluorine-based acrylic polymer is preferably 50 to 100 mass%, more preferably 55 to 100 mass%, and even more preferably 60 to 100 mass%, based on the total amount of the monomer components constituting the non-fluorine-based polymer, from the viewpoint of the water repellency and durable water repellency of the resulting textile product.

[0111] In order to further improve the water repellency of the resulting textile product and the emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the non-fluorinated acrylic polymer, it is preferable that the non-fluorinated acrylic polymer contains, in addition to component (A), at least one reactive emulsifier (B) (hereinafter also referred to as "component (B)") selected from the group consisting of: (B1) a compound represented by general formula (I-1) below and having an HLB of 7 to 18; (B2) a compound represented by general formula (II-1) below and having an HLB of 7 to 18; and (B3) a compound formed by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having a hydroxy group and a polymerizable unsaturated group, having an HLB of 7 to 18.

[0112] [ka]

[0113] [In formula (I-1), R 3 represents hydrogen 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.

[0114] [ka]

[0115] [In formula (II-1), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group, and Y 2 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.

[0116] The term "reactive emulsifier" refers to an emulsifying dispersant having radical reactivity, i.e., 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.

[0117] The HLB of the compounds (B1) to (B3) used in this embodiment is 7 to 18, and from the viewpoint of emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the non-fluorinated acrylic polymer (hereinafter simply referred to as emulsion stability), it is preferably 9 to 15. Furthermore, from the viewpoint of storage stability of the surface treatment agent composition, it is more preferable to use in combination two or more reactive emulsifiers (B) having different HLBs within the above range.

[0118] In the reactive emulsifier (B1) represented by the general formula (I-1) used in this embodiment, R 3 is hydrogen or a methyl group, and is more preferably a methyl group in terms of copolymerizability with component (A). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and is more preferably a linear alkylene group having 2 to 3 carbon atoms in terms of emulsion stability of the non-fluorinated acrylic polymer of this embodiment. 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.

[0119] As the compound represented by the above general formula (I-1), a compound represented by the following general formula (I-2) is preferred.

[0120] [ka]

[0121] [In formula (I-2), R 3 represents hydrogen 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, and m can be appropriately selected so as to fall within the above HLB range. Specifically, an integer of 1 to 80 is preferred. When m is 2 or more, m A 1 O may be the same or different.]

[0122] In the compound represented by the above general formula (I-2), R 3 is hydrogen or a methyl group, and is preferably a methyl group in terms of copolymerizability with component (A). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and is more preferably a linear alkylene group having 2 to 3 carbon atoms in terms of emulsion stability of the non-fluorinated acrylic polymer. A 1 O is an alkyleneoxy group having 2 to 4 carbon atoms. 1 The 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 emulsion stability of the non-fluorine acrylic polymer, m is preferably an integer of 1 to 80, 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.

[0123] The reactive emulsifier (B1) represented by the general formula (I-2) can be obtained by a conventionally known method and is not particularly limited. It can also be easily obtained from commercial products, such as "Latemul PD-420," "Latemul PD-430," and "Latemul PD-450" manufactured by Kao Corporation.

[0124] In the reactive emulsifier (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 tetradecadienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group, and a heptadecatrienyl group. In terms of emulsion stability of non-fluorinated polymers, R 4 is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

[0125] Y 2is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. 2 The type, combination, and number of alkyleneoxy groups in the above formula (1) can 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. In terms of emulsion stability of the non-fluorine-containing acrylic polymer, the alkyleneoxy group is preferably an ethyleneoxy group.

[0126] The compound represented by the above general formula (II-1) is preferably a compound represented by the following general formula (II-2).

[0127] [ka]

[0128] [In formula (II-2), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group, and A 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n can be appropriately selected so as to fall within the above HLB range. Specifically, an integer of 1 to 50 is preferred. When n is 2 or more, n A 2 O may be the same or different.]

[0129] 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.

[0130] A 2 O is an alkyleneoxy group having 2 to 4 carbon atoms. In terms of emulsion stability of non-fluorine acrylic polymers, 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. 2O 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 further 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.

[0131] The reactive emulsifier (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 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.

[0132] Phenols having the corresponding unsaturated hydrocarbon group include pure products or mixtures produced industrially, as well 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 and are collectively known as cardanol.

[0133] The reactive emulsifier (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 hydroxy group and a polymerizable unsaturated group, and the fat or oil has an HLB value of 7 to 18. Examples of the fat or oil having a hydroxy group and a polymerizable unsaturated group include mono- or diglycerides of fatty acids that may contain unsaturated 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, ricinoelaidic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of emulsion stability of the non-fluorinated polymer, 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 emulsion stability of the non-fluorinated acrylic polymer, 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.

[0134] The reactive emulsifier (B3) used in this embodiment can be synthesized by adding an alkylene oxide to a fat or oil having a hydroxy 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.

[0135] From the viewpoint of further improving the water repellency of the obtained textile product and the emulsion stability of the non-fluorinated acrylic polymer, the constituent ratio of the monomer of component (B) in the non-fluorinated acrylic polymer is preferably from 0.5 to 20 mass%, more preferably from 1 to 15 mass%, and even more preferably from 3 to 10 mass%, relative to the total amount of monomer components constituting the non-fluorinated acrylic polymer.

[0136] In order to further improve the durable water repellency of the resulting textile product, the non-fluorinated acrylic polymer preferably contains, in addition to the component (A), at least one second (meth)acrylic acid ester monomer (C) (hereinafter also referred to as "component (C)") selected from the group consisting of the following (C1), (C2), (C3), (C4) and (C5) as a monomer component.

[0137] (C1) is a (meth)acrylic acid ester monomer other than (C5) and represented by the following general formula (C-1).

[0138] [ka]

[0139] [In formula (C-1), R 5 represents hydrogen or a methyl group, and 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 hydroxy group, an amino group, a carboxy 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.]

[0140] (C2) is a (meth)acrylic acid ester monomer represented by the following general formula (C-2).

[0141] [ka]

[0142] [In formula (C-2), R7 represents hydrogen or a methyl group, and R 8 represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent.]

[0143] (C3) is a methacrylic acid ester monomer represented by the following general formula (C-3).

[0144] [ka]

[0145] [In formula (C-3), R 9 represents an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms.]

[0146] (C4) is a (meth)acrylic acid ester monomer represented by the following general formula (C-4).

[0147] [ka]

[0148] [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.]

[0149] (C5) is a (meth)acrylic acid ester monomer represented by the following general formula (C-5).

[0150] [ka]

[0151] [In formula (C-5), R 11 represents hydrogen or a methyl group, and R 12 represents a monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms and having a hydroxy group and at least one functional group selected from the group consisting of a chloro group and a bromo group.]

[0152] The monomer (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 hydroxy group, an amino group, a carboxy group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group in the ester moiety, and is a (meth)acrylic acid ester monomer other than the monomer (C5). From the viewpoint of being reactive 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 hydroxy group, an amino group, a carboxy group, an epoxy group, and an isocyanate group. When a non-fluorine-containing acrylic polymer containing the monomer (C1) having a group reactive with such a crosslinking agent is applied to a textile product together with the crosslinking agent, the durable water repellency of the resulting textile product can be further improved while maintaining its texture. The isocyanate group may be a blocked isocyanate group protected with a blocking agent.

[0153] 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 further improving the durable water repellency of the resulting textile product.

[0154] Specific examples of the monomer (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 them, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferred in terms of further improving the durable water repellency of the resulting textile product. Furthermore, dimethylaminoethyl (meth)acrylate is preferred in terms of further improving the texture of the resulting textile product.

[0155] The proportion of the monomer (C1) in the non-fluorine-based acrylic polymer is preferably from 1 to 30 mass%, more preferably from 3 to 25 mass%, and even more preferably from 5 to 20 mass%, based on the total amount of monomer components constituting the non-fluorine-based acrylic polymer, from the viewpoint of water repellency and texture of the resulting textile product.

[0156] The monomer (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 further improving durable water repellency, it is preferable that these cyclic hydrocarbon groups are 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 further improve the durable water repellency of the resulting textile product.

[0157] The proportion of the monomer (C2) in the non-fluorine-based acrylic polymer is preferably from 1 to 30 mass%, more preferably from 3 to 25 mass%, and even more preferably from 5 to 20 mass%, based on the total amount of monomer components constituting the non-fluorine-based acrylic polymer, from the viewpoint of water repellency and texture of the resulting textile product.

[0158] The monomer (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 that they can further improve the durable water repellency of the resulting textile product.

[0159] The proportion of the monomer (C3) in the non-fluorine-based acrylic polymer is preferably from 1 to 30 mass%, more preferably from 3 to 25 mass%, and even more preferably from 5 to 20 mass%, based on the total amount of monomer components constituting the non-fluorine-based polymer, from the viewpoint of water repellency and texture of the resulting textile product.

[0160] The monomer (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 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 that they can further improve the durable water repellency of the resulting textile product.

[0161] The proportion of the monomer (C4) in the non-fluorine-based acrylic polymer is preferably from 1 to 30 mass%, more preferably from 3 to 25 mass%, and even more preferably from 5 to 20 mass%, based on the total amount of monomer components constituting the non-fluorine-based acrylic polymer, from the viewpoint of water repellency and texture of the resulting textile product.

[0162] The monomer (C5) has a monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms and having at least one functional group selected from the group consisting of a chloro group and a bromo group and a hydroxy group. 11 is hydrogen or a methyl group. In terms of the durable water repellency of the resulting textile product, R 11 is preferably a methyl group.

[0163] R 12is a monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms and having at least one functional group selected from the group consisting of a chloro group and a bromo group and a hydroxy group. The chain saturated hydrocarbon group may be linear or branched. When the chain saturated hydrocarbon group is linear, the durable water repellency of the resulting textile product is superior. The number of carbon atoms in the chain saturated hydrocarbon group is preferably 3 to 4, and more preferably 3, from the viewpoint of durable water repellency of the resulting textile product.

[0164] From the viewpoint of durable water repellency of the resulting textile product, the above-mentioned chain saturated hydrocarbon group preferably has one or two chloro groups and one hydroxy group, and more preferably has one chloro group and one hydroxy group. Also, from the viewpoint of durable water repellency of the resulting textile product, the chain saturated hydrocarbon group has a β-position (CH2=CR 11 It is more preferable that the chain saturated hydrocarbon group has a hydroxy group on the carbon atom adjacent to the carbon atom bonded to (CO)O-. Specific examples of the chain saturated hydrocarbon group include a 3-chloro-2-hydroxypropyl group, a 3-chloro-2-hydroxybutyl group, a 5-chloro-2-hydroxypentyl group, a 3-chloro-2-hydroxy-2-methylpropyl group, and a 3-bromo-2-hydroxypropyl group.

[0165] Specific examples of the monomer (C5) include 3-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxybutyl (meth)acrylate, 5-chloro-2-hydroxypentyl (meth)acrylate, and 3-bromo-2-hydroxypropyl (meth)acrylate. Among these, 3-chloro-2-hydroxypropyl (meth)acrylate is preferred, and 3-chloro-2-hydroxypropyl methacrylate is more preferred, in that it can further improve the durable water repellency of the resulting textile product.

[0166] In terms of durable water repellency of the resulting textile product, the constituent ratio of the (C5) monomer in the non-fluorine-based acrylic polymer is preferably from 1 to 30 mass %, more preferably from 3 to 25 mass %, and even more preferably from 5 to 20 mass %, based on the total amount of monomer components constituting the non-fluorine-based acrylic polymer.

[0167] From the viewpoint of water repellency and texture of the resulting textile product, the total constituent ratio of the monomers of component (C) in the non-fluorine-based acrylic polymer is preferably from 1 to 30 mass%, more preferably from 3 to 25 mass%, and even more preferably from 5 to 20 mass%, based on the total amount of monomer components constituting the non-fluorine-based acrylic polymer.

[0168] The fluorine-free acrylic polymer may contain, in addition to the components (A), (B), and (C), a monofunctional monomer (D) copolymerizable with these components (D) (hereinafter also referred to as "component (D)"), within the range that does not impair the effects of the present invention.

[0169] Examples of the monomer (D) include (meth)acryloylmorpholine, (meth)acrylic acid esters having a hydrocarbon group other than components (A) and (C), (meth)acrylic acid, fumaric acid esters, maleic acid esters, fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene, styrene, and other fluorine-free vinyl monomers other than component (E) described below. Note that the (meth)acrylic acid esters having a hydrocarbon group other than components (A) and (C) may have a substituent on the hydrocarbon group such as a vinyl group, a hydroxy 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, a urethane bond, or the like. Examples of (meth)acrylic acid esters other than the components (A) and (C) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and ethylene glycol di(meth)acrylate.

[0170] The proportion of the monomer of component (D) in the non-fluorine-based acrylic polymer is preferably 10 mass % or less based on the total amount of monomer components constituting the non-fluorine-based acrylic polymer, from the viewpoint of water repellency and texture of the obtained textile product.

[0171] The non-fluorine-containing acrylic polymer preferably has at least one functional group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an epoxy group, and an isocyanate group that can react with a crosslinking agent, since this further improves the durable water repellency of the resulting textile product. The isocyanate group may be protected with a blocking agent to form a blocked isocyanate group. The non-fluorine-containing acrylic polymer preferably has an amino group, since this further improves the texture of the resulting textile product.

[0172] The non-fluorinated acrylic polymer preferably contains, in addition to component (A), at least one monomer (E) of vinyl chloride and vinylidene chloride (hereinafter also referred to as "component (E)") as a monomer component, in order to further improve the water repellency and peel strength against coating of the obtained textile product.

[0173] The at least one monomer (E) of vinyl chloride and vinylidene chloride used in this embodiment is preferably vinyl chloride in terms of the water repellency of the resulting textile product and the peel strength against coating.

[0174] From the viewpoint of further improving the peel strength of the resulting textile product against coating, the constituent proportion of the monomer of component (E) in the fluorine-free acrylic polymer is preferably 1 to 45 mass%, more preferably 3 to 40 mass%, and even more preferably 5 to 35 mass%, relative to the total amount of monomer components constituting the fluorine-free acrylic polymer.

[0175] A method for producing the above-mentioned fluorine-free acrylic polymer will now be described.

[0176] The fluorine-free acrylic polymer can be produced by radical polymerization. Among these radical polymerization methods, emulsion polymerization or dispersion polymerization is preferred from the viewpoints of the performance of the resulting surface treatment agent and the environment.

[0177] For example, a non-fluorinated acrylic polymer can be obtained by emulsion polymerization or dispersion polymerization of a (meth)acrylic acid ester monomer (A) represented by the above general formula (A-1) in a medium. More specifically, for example, component (A) and, if necessary, components (B), (C), (D), and (E), as well as an emulsifying aid or dispersing aid, are added to a medium, and the resulting mixture is emulsified or dispersed to obtain an emulsion or dispersion. A polymerization initiator is added to the resulting emulsion or dispersion to initiate a polymerization reaction, thereby polymerizing the monomer and reactive emulsifier. Examples of means for emulsifying or dispersing the above-mentioned mixture include a homomixer, a high-pressure emulsifier, and ultrasound.

[0178] The emulsifying aid or dispersing aid (hereinafter also referred to as "emulsifying aid") can be one or more selected from nonionic surfactants other than the reactive emulsifier (B), cationic surfactants, anionic surfactants, and amphoteric surfactants. The content of the emulsifying aid is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total monomers. When the content of the emulsifying aid is 0.5 parts by mass or more, the dispersion stability of the mixed liquid tends to be further improved, and when the content of the emulsifying aid is 30 parts by mass or less, the water repellency of the resulting surface treatment agent composition tends to be further improved.

[0179] The medium for emulsion polymerization or dispersion polymerization is preferably water, and water may be mixed with an organic solvent as needed. Examples of the organic solvent include alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, and glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol. The ratio of water to the organic solvent is not particularly limited.

[0180] As the polymerization initiator, known polymerization initiators such as azo-based, peroxide-based, or redox-based initiators can be used as appropriate. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass per 100 parts by mass of all monomers. When the content of the polymerization initiator is within the above range, a non-fluorine-containing acrylic polymer having a weight-average molecular weight of 10,100,000 or more can be efficiently produced.

[0181] In the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or t-butyl alcohol may be used for the purpose of adjusting the molecular weight.

[0182] A polymerization inhibitor may be used to adjust the molecular weight, and the addition of a polymerization inhibitor makes it possible to easily obtain a fluorine-free acrylic polymer having a desired weight average molecular weight.

[0183] The temperature of the polymerization reaction is preferably 20° C. to 150° C. If the temperature is 20° C. or higher, the polymerization tends to be sufficient, and if the temperature is 150° C. or lower, the reaction heat tends to be easily controlled.

[0184] In the polymerization reaction, the weight average molecular weight of the resulting non-fluorinated acrylic polymer can be adjusted by increasing or decreasing the contents of the above-mentioned polymerization initiator, chain transfer agent, and polymerization inhibitor, and the melt viscosity at 105°C can be adjusted by increasing or decreasing the content of the polyfunctional monomer and the content of the polymerization initiator. Note that, when it is desired to decrease the melt viscosity at 105°C, the content of the monomer having two or more polymerizable functional groups can be decreased or the content of the polymerization initiator can be increased.

[0185] The content of the non-fluorinated acrylic polymer in the polymer emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization is preferably 10 to 50 mass %, more preferably 20 to 40 mass %, based on the total amount of the emulsion or dispersion, from the viewpoints of storage stability and handleability of the composition.

[0186] Examples of the hydrocarbon group-containing compounds include Neoseed NR-90 (manufactured by Nicca Chemical Co., Ltd.), NR-158 (manufactured by Nicca Chemical Co., Ltd.), NR-7080 (manufactured by Nicca Chemical Co., Ltd.), TH-44 (manufactured by Nicca Chemical Co., Ltd.), PW-182 (manufactured by Yamato Chemical Co., Ltd.), Forbor, RSH (manufactured by Huntsman Japan Co., Ltd.), Palladium ECO-500 (manufactured by Ohara Palladium Chemical Co., Ltd.), and NX018 (manufactured by Nanotex Co., Ltd.).

[0187] <Other ingredients> In addition to the components described above, the surface treatment agent composition of the present embodiment may further contain a surfactant, an antifoaming agent, an organic acid, an inorganic acid, an alcohol, an antibacterial agent, an antifungal agent, a pH adjuster, a colorant, silica, an antioxidant, a deodorizer, various catalysts, emulsion stabilizers, various organic solvents, a chelating agent, an antistatic agent, an organo-modified silicone other than a silanol-modified silicone, a crosslinking agent other than a polyfunctional isocyanate, and the like.

[0188] The surfactant essentially contains a polyalkylene oxide adduct, and may further contain other surfactants. For example, the other surfactants may be those that serve to expand the temperature range in which the emulsion state is stably maintained and to adjust the amount of foaming that occurs when the emulsion is mixed with water to prepare a diluted solution. The other surfactants may be any of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. The other surfactants may be used alone or in combination of two or more.

[0189] The defoaming agent is not particularly limited, and examples thereof include oil-based defoaming agents such as castor oil, sesame oil, linseed oil, and animal and vegetable oils; fatty acid-based defoaming agents such as stearic acid, oleic acid, and palmitic acid; fatty acid ester-based defoaming agents such as isoamyl stearate, distearyl succinate, ethylene glycol distearate, and butyl stearate; and olefin-based defoaming agents such as polyoxyalkylene monohydric alcohol, di-t-amylphenoxyethanol, 3-heptanol, and 2-ethylhexanol. Examples of suitable antifoaming agents include alcohol-based antifoaming agents, ether-based antifoaming agents such as di-t-amylphenoxyethanol, 3-heptyl cellosolve, nonyl cellosolve, and 3-heptyl carbitol, phosphate-based antifoaming agents such as tributyl phosphate and tris(butoxyethyl) phosphate, amine-based antifoaming agents such as diamylamine, amide-based antifoaming agents such as polyalkylene amide and acylate polyamine, sulfate-based antifoaming agents such as sodium lauryl sulfate, and mineral oil. These antifoaming agents can be used singly or in combination of two or more.

[0190] The organic acid is not particularly limited, and examples thereof include lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, methanesulfonic acid, toluenesulfonic acid, etc. The organic acids can be used alone or in combination of two or more.

[0191] The inorganic acid is not particularly limited, and examples thereof include hydrogen chloride, sulfuric acid, nitric acid, etc. The inorganic acids may be used alone or in combination of two or more.

[0192] The alcohol is not particularly limited, and examples thereof include ethanol, isopropanol, glycerin, trimethylolpropane, diethylene glycol, triethylene glycol, dipropylene glycol, propylene glycol, etc. The alcohols can be used alone or in combination of two or more.

[0193] It is preferable to use an antistatic agent that does not easily impair water-repellent performance. Examples of antistatic agents include cationic surfactants such as higher alcohol sulfates, sulfated oils, sulfonates, quaternary ammonium salts, and imidazoline-type quaternary salts; nonionic surfactants such as polyethylene glycols and polyhydric alcohol esters; amphoteric surfactants such as imidazoline-type quaternary salts, alanine types, and betaine types; and polymer compound types such as the antistatic polymers and polyalkylamines described above. Antistatic agents can be used alone or in combination of two or more.

[0194] Examples of crosslinking agents other than the polyfunctional isocyanates include melamine resins and glyoxal resins.

[0195] The melamine resin may be a compound having a melamine skeleton, such as polymethylolmelamines such as trimethylolmelamine and hexamethylolmelamine; alkoxymethylmelamines in which some or all of the methylol groups of polymethylolmelamine are alkoxymethyl groups having an alkyl group containing 1 to 6 carbon atoms; and acyloxymethylmelamines in which some or all of the methylol groups of polymethylolmelamine are acyloxymethyl groups having an acyl group containing 2 to 6 carbon atoms. These melamine resins may be either a monomer or a dimer or higher polymer, or a mixture thereof. Furthermore, melamine resins in which urea or the like is co-condensed with a portion of the melamine may also be used. Examples of such melamine resins include Beckamine APM, Beckamine M-3, Beckamine M-3(60), Beckamine MA-S, Beckamine J-101, and Beckamine J-101LF manufactured by DIC Corporation, Unika Resin 380K manufactured by Union Chemical Industry Co., Ltd., and Riken Resin MM series manufactured by Miki Riken Kogyo Co., Ltd.

[0196] Conventional glyoxal resins can be used. Examples of glyoxal resins include 1,3-dimethylglyoxal urea resins, dimethylol dihydroxyethylene urea resins, and dimethylol dihydroxypropylene urea resins. The functional groups of these resins may be substituted with other functional groups. Examples of such glyoxal resins include Beckamine N-80, Beckamine NS-11, Beckamine LF-K, Beckamine NS-19, Beckamine LF-55P Concentrate, Beckamine NS-210L, Beckamine NS-200, and Beckamine NF-3, all manufactured by DIC Corporation; Uniresin GS-20E, manufactured by Union Chemical Industry Co., Ltd.; and Rikenresin RG series and Rikenresin MS series, all manufactured by Miki Riken Kogyo Co., Ltd.

[0197] It is preferable to use a catalyst for melamine resins and glyoxal resins in order to promote the reaction. Such catalysts are not particularly limited as long as they are commonly used catalysts, and examples include borofluoride compounds such as ammonium borofluoride and zinc borofluoride; neutral metal salt catalysts such as magnesium chloride and magnesium sulfate; and inorganic acids such as phosphoric acid, hydrochloric acid, and boric acid. These catalysts can also be used in combination with organic acids such as citric acid, tartaric acid, malic acid, maleic acid, and lactic acid as promoters, if necessary. Examples of such catalysts include Catalyst ACX, Catalyst 376, Catalyst O, Catalyst M, Catalyst G (GT), Catalyst X-110, Catalyst GT-3, and Catalyst NFC-1 manufactured by DIC Corporation; Unika Catalyst 3-P and Unika Catalyst MC-109 manufactured by Union Chemical Industry Co., Ltd.; and Riken Fixer RC series, Riken Fixer MX series, and Riken Fixer RZ-5 manufactured by Miki Riken Kogyo Co., Ltd.

[0198] The surface treatment agent composition according to the present embodiment described above can be suitably used for applications such as textile product processing agents, paper product processing agents, and leather product processing agents.

[0199] <Method for producing surface treatment composition> The present embodiment also provides a method for producing the surface treatment agent composition of the present embodiment. The surface treatment agent composition of the present embodiment can be produced by emulsifying and dispersing the components described above for the composition. For example, the surface treatment agent composition can be obtained by dissolving a silicone resin and a silanol-modified silicone in an organic solvent, and then emulsifying and dispersing the resulting composition using an emulsifier and an aqueous medium (an emulsified dispersion of a silicone resin and a silanol-modified silicone). In one aspect, a method for producing a surface treatment agent composition is provided, which includes mixing a silicone resin (A), an organopolysiloxane (B) containing silanol groups, and a hydrophobic organic solvent. In another aspect, a method for producing a surface treatment agent composition is provided, which includes mixing a silicone resin (A), an organopolysiloxane (B) containing silanol groups, and an alkylpolysiloxane.

[0200] Alternatively, the silicone resin can be dissolved in an organic solvent with heating, and then the silanol-modified silicone and alkylpolysiloxane are added and stirred to achieve a uniform mixture. This method is suitable for applications that are difficult to handle with aqueous systems, such as hard surfaces other than textiles, paper, and cardboard.

[0201] When the surface treatment agent composition contains at least one selected from the group consisting of alkyl polysiloxanes, non-fluorine acrylic polymers, and polyfunctional isocyanates, it can be obtained by dissolving a silicone resin; a silanol-modified silicone; and at least one selected from alkyl polysiloxanes, non-fluorine acrylic polymers, and polyfunctional isocyanates in an organic solvent, and then emulsifying and dispersing the mixture using an emulsifier and an aqueous medium.

[0202] When the surface treatment agent composition contains at least one selected from the group consisting of alkyl polysiloxanes, non-fluorine-based acrylic polymers, and polyfunctional isocyanates, it may be a one-component type in which a silicone resin, a silanol-modified silicone, and at least one selected from the group consisting of alkyl polysiloxanes, non-fluorine-based acrylic polymers, and polyfunctional isocyanates are pre-mixed, or it may be a two-component type, a three-component type, a four-component type, etc. in which, for example, an emulsified dispersion of the silicone resin and the silanol-modified silicone and an emulsified dispersion obtained by dissolving at least one selected from the group consisting of alkyl polysiloxanes, non-fluorine-based acrylic polymers, and polyfunctional isocyanates in an organic solvent and then emulsifying and dispersing the resultant using an emulsifier and an aqueous medium. These may be mixed to prepare the surface treatment agent composition, or further treated with a high-pressure homogenizer or the like to prepare the surface treatment agent composition. From the viewpoint of ease of handling, the surface treatment agent composition of this embodiment is preferably a one-component or two-component type.

[0203] A method for dispersing each of the above components in an aqueous medium can be, for example, mixing and stirring each component, the organic solvent of this embodiment, the aqueous medium of this embodiment, and the emulsifier of this embodiment. When mixing and stirring, a conventionally known emulsifying disperser such as a Milder, a high-speed mixer, a homogenizer, an ultrasonic homogenizer, a homomixer, a bead mill, a pearl mill, a Dyno Mill, an Aspek Mill, a basket mill, a ball mill, a Nanomizer, an Ultimizer, or a Starburst may be used. These emulsifying dispersers can be used alone or in combination of two or more.

[0204] As the aqueous medium, various organic solvents exemplified in the above section <Aqueous Medium> can be used. The aqueous medium may be contained in the surface treatment agent composition as a mixed solvent with water.

[0205] The dispersion may further contain a surfactant from the viewpoint of dispersion stability. Such surfactants are not particularly limited as long as they can improve emulsion dispersion stability, and examples thereof include known nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. These surfactants may be used alone or in combination of two or more.

[0206] The surface treatment agent composition in the form of the dispersion may be used as a treatment liquid as is, or may be further diluted with an aqueous medium or a hydrophobic organic solvent to form a treatment liquid. In one embodiment, the surface treatment agent composition or treatment liquid may contain a silicone resin, a silanol-modified silicone, and an alkylpolysiloxane in a total amount of, for example, 0.5 to 80 mass%, or 1 to 50 mass%, or 1.5 to 45 mass%. The treatment liquid may contain a polyfunctional isocyanate and other crosslinking agents in a total amount of, for example, 0.1 to 5.0 mass%, or 0.2 to 3.0 mass%, or 0.3 to 2.0 mass%.

[0207] Substrates that can be used in the present disclosure may be made of any suitable material, such as glass, resin (which may be a natural or synthetic resin, for example, a common plastic material), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., building materials, etc., sanitary products, etc.

[0208] <Water- and oil-repellent textile products and their manufacturing methods> The present embodiment further provides a water- and oil-repellent textile product and a manufacturing method thereof. In one aspect, a water- and oil-repellent textile product is provided, which has a textile product and the surface treatment agent composition of the present embodiment adhered to the textile product. In one aspect, the water- and oil-repellent textile product of the present embodiment can be manufactured by a method including a step of treating the textile product with a treatment liquid containing the surface treatment agent composition of the present embodiment described above. In one aspect, the water- and oil-repellent textile product is obtained by treating a textile product with the surface treatment agent composition of the present embodiment (i.e., by water- and oil-repellent treatment). In one aspect, the water- and oil-repellent textile product contains the silicone resin and silanol-modified silicone described above as components of the surface treatment agent composition, and optionally further contains one or more of the hydrophobic organic solvent, alkylpolysiloxane, polyfunctional isocyanate, and other components described above as components of the surface treatment agent composition.

[0209] The fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as nylon, polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The fiber may be in the form of any of yarn, cloth, nonwoven fabric, paper, and the like. The fiber may also be a textile product.

[0210] Examples of methods for treating fibers with a treatment liquid containing the surface treatment agent composition of this embodiment include, for example, a one-step treatment method using a treatment liquid containing a silicone resin, a silanol-modified silicone, and at least one selected from the group consisting of an alkylpolysiloxane, a non-fluorine-containing acrylic polymer, and a polyfunctional isocyanate when the surface treatment agent composition contains a silicone resin, a silanol-modified silicone, and at least one selected from the group consisting of an alkylpolysiloxane, a non-fluorine-containing acrylic polymer, and a polyfunctional isocyanate, and a two-step, three-step, four-step, or five-step treatment method using a treatment liquid containing at least one of the above components and a treatment liquid containing at least one other component. When treating in two to five steps, the order in which the respective components are treated may be any order.

[0211] Examples of methods for treating fibers with the treatment liquid include immersion, spraying, coating, etc. When the surface treatment agent composition contains water, it is preferable to dry the fiber after it has been applied to the fiber to remove the water.

[0212] The amount of the surface treatment composition of this embodiment attached to the fiber can be adjusted as appropriate depending on the required level of water repellency. It is preferable to adjust the amount of the surface treatment composition attached (in one embodiment, the total amount of silicone resin, silanol-modified silicone, and alkylpolysiloxane attached) to 0.1 to 5 g, and more preferably 0.1 to 3 g, per 100 g of fiber. If the amount of the surface treatment composition attached is less than 0.1 g, the fiber tends not to exhibit sufficient water repellency, and if it exceeds 5 g, it tends to be economically disadvantageous. The amount attached can be confirmed, for example, by solvent extraction from the textile product.

[0213] After the surface treatment composition of the present embodiment is applied to the fibers, it is preferable to appropriately perform a heat treatment. The temperature conditions are not particularly limited, but from the viewpoints of water repellency, durable water repellency, and texture, it is preferable to perform the heat treatment at 110 to 180°C for 1 to 5 minutes.

[0214] The water- and oil-repellent textile product of the present embodiment exhibits excellent water repellency and a soft texture, and is therefore suitable for textile applications such as clothing and non-clothing applications, such as down coverings, coats, blousons, windbreakers, blouses, dress shirts, skirts, slacks, gloves, hats, futon coverings, futon drying rack covers, curtains, and tents. [Example]

[0215] 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.

[0216] <Production of Silicone Dispersion> [Materials used] (Silicone resin) MQ-1600: Manufactured by Dow Chemical, weight average molecular weight (GPC measurement result) 6,500

[0217] (organic solvent) Isoparaffin: IP-2028, manufactured by Idemitsu Kosan Co., Ltd., isoparaffin with 10 to 16 carbon atoms. The amount of water required to dissolve 1 g of organic solvent: more than 1000 mL Isododecane: Macazol R (Maruzen Petrochemical Co., Ltd.) The amount of water required to dissolve 1 g of organic solvent: more than 1000 mL

[0218] (Alkylpolysiloxane) Dimethyl silicone 1: DOWSIL TM SH 200 Fluid 0.5 cSt (Dow Toray Industries, Inc.), viscosity measured according to JIS K2283:2000 (Ubbelohde viscometer) (25°C): 0.5 mm 2 / s Dimethyl silicone 2: DOWSIL TM SH 200 Fluid 100cSt (Dow Toray Industries, Inc.), viscosity measured according to JIS K2283:2000 (Ubbelohde viscometer) (25°C): 100mm 2 / s Dimethyl silicone 3: DOWSIL TM SH 200 Fluid 1000cSt (Dow Toray Industries, Inc.), viscosity measured according to JIS K2283:2000 (Ubbelohde viscometer) (25°C): 1000mm 2 / s

[0219] (Silanol-modified silicone) Silanol-modified silicone: KF-9701 (Shin-Etsu Chemical Co., Ltd.), functional group equivalent: 1500 g / mol In formula (1), X = OH, n = 38.3, R = methyl group, kinematic viscosity at 25 ° C. 60 mm 2 / s

[0220] (Other modified silicones) Amino-modified silicone: KF-8010 (Shin-Etsu Chemical Co., Ltd.), functional group equivalent: 430 g / mol Epoxy-modified silicone: KF-105 (Shin-Etsu Chemical Co., Ltd.), functional group equivalent: 490 g / mol Polyether-modified silicone: KF-6123 (Shin-Etsu Chemical Co., Ltd.), functional group equivalent: 1120 g / mol Carboxy-modified silicone: X-22-162C (Shin-Etsu Chemical Co., Ltd.), functional group equivalent: 2300 g / mol

[0221] (Emulsifier: Nonionic surfactant) Polyoxyethylene (7 moles) isodecyl ether: A synthetic product obtained by adding ethylene oxide (7 moles) to isodecyl alcohol (1 mole) according to the usual method. HLB: 13.2 Polyoxyethylene (9 moles) isodecyl ether: A synthetic product obtained by adding ethylene oxide (9 moles) to isodecyl alcohol (1 mole) according to the usual method. HLB: 14.3 (Emulsifier: Cationic surfactant) Lipocard T-28: Stearyltrimethylammonium chloride manufactured by Lion Corporation (Emulsifier: amphoteric surfactant) Anhithol 86B: Kao stearyl betaine

[0222] <Production of Silicone Dispersion> [Manufacturing Example 1] 200 g of isododecane and 90 g of MQ-1600 (silicone resin) were added to a flask and dissolved by heating at 80° C. Furthermore, 160 g of KF-9701 (silanol-modified silicone) was added to obtain a silicone dispersion (solid content 56% by mass).

[0223] [Manufacturing Examples 2 and 3] A silicone dispersion was obtained by carrying out the same procedure as in Production Example 1, except that the formulation was as shown in Table 1.

[0224] [Manufacturing Example 4] A silicone dispersion was obtained by carrying out the same procedure as in Production Example 3, except that isododecane was replaced with alkylpolysiloxane in the formulation shown in Table 1.

[0225] [Manufacturing Example 5] A silicone dispersion was obtained by carrying out the same procedure as in Production Example 3, except that isododecane was replaced with isododecane and alkylpolysiloxane in the formulation shown in Table 1.

[0226] [Comparative Manufacturing Example 1] A silicone dispersion was obtained in the same manner as in Production Example 5, except that the silanol-modified silicone was replaced with an amino-modified silicone in the formulation shown in Table 1.

[0227] [Comparative Manufacturing Example 2] Silicone dispersions were obtained by carrying out the same procedure as in Production Example 5, except that the amount of silicone resin was changed as shown in Table 1 and no silanol-modified silicone was added.

[0228] [Comparative Manufacturing Example 3] 100 g of alkylpolysiloxane and 100 g of isododecane were placed in a flask, and 250 g of silanol-modified silicone was added at 60° C. to obtain a silicone dispersion.

[0229] [Manufacturing Example 6] 100 g of isoparaffin and 141 g of MQ-1600 (silicone resin) were added to a flask and dissolved while heating at 80°C. Furthermore, 108 g of dimethylsilicone 2 (alkylpolysiloxane) and 1 g of KF-9701 (silanol-modified silicone) were added at 80°C and stirred to homogenize. 30 g of polyoxyethylene (7 mol) isodecyl ether (nonionic surfactant), 5 g of polyoxyethylene (9 mol) isodecyl ether (nonionic surfactant), 5 g of Lipocard T-28 (cationic surfactant), and pure water were added to the mixture, and the mixture was treated at 300 bar with a high-pressure homogenizer (APV Gaulin Inc., Model 15MR-8TBA) to obtain a dispersion containing a total of 25% by mass of silicone resin, silanol-modified silicone, and alkylpolysiloxane as surface treatment components.

[0230] [Production Examples 7 to 16, Comparative Production Examples 4 to 8] A dispersion containing a total of 25 mass% of silicone resin, silanol-modified silicone (or modified silicone), and alkylpolysiloxane as surface treatment components was obtained by performing the same operation as in Production Example 6, except that the formulation was as shown in Table 3. In Comparative Production Examples 4 to 7, each modified silicone shown in Table 3 was used instead of silanol-modified silicone, and in Comparative Production Example 8, no silanol-modified silicone was added.

[0231] [Comparative Production Example 9] 100 g of isoparaffin was placed in a flask, and 108 g of dimethylsilicone 2 (alkylpolysiloxane) and 142 g of KF-9701 (silanol-modified silicone) were added, followed by stirring at 60° C. to homogeneously mix. Polyoxyethylene, a cationic surfactant, and pure water were added thereto in the same manner as in Production Example 6, and the mixture was treated with a high-pressure homogenizer to obtain a dispersion containing a total of 25 mass% of silanol-modified silicone and alkylpolysiloxane as surface treatment components.

[0232] <Production of Crosslinking Component Dispersion> [Crosslinked component dispersion 1] (Hexamethylene diisocyanate (HDI) biuret dimethylpyrazole (DMP) block compound) One mole of Duranate 24A-100 (biuret type hexamethylene diisocyanate, NCO functionality: 3, content: 100% by mass, product name: Asahi Kasei Chemicals Corporation) and methyl isobutyl ketone were added to a reaction vessel and heated to 60 to 70°C. Next, 3 moles of 3,5-dimethylpyrazole were slowly added, and the reaction was continued at 60 to 70°C until the isocyanate content, as confirmed by infrared spectrophotometer, reached zero, thereby obtaining a colorless, transparent, viscous liquid composition containing 98.7% by mass of a dimethylpyrazole-blocked polyisocyanate compound.

[0233] 180 parts by mass of the composition obtained above, 140 parts by mass of butyl diglycol as an organic solvent, and 20 parts by mass of an ethylene oxide 30 mole adduct of 3-styrenated phenol as a nonionic surfactant were mixed and homogenized. Water was gradually added while stirring, and then the mixture was homogenized at 30 MPa to obtain a crosslinking component dispersion 1 containing 20% ​​by mass of a dimethylpyrazole block compound of hexamethylene diisocyanate biuret.

[0234] [Crosslinked component dispersion 2] (Dimethylpyrazole (DMP) blocked isophorone diisocyanate (IPDI) trimer) In a reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 150 g (NCO equivalent: 0.62 mol) of Vestanat 1890 / 100 (isophorone diisocyanate (IPDI) trimer, manufactured by Evonik, NCO group content: 17.3%, NV: 100%) and 150 g of diethylene glycol ethyl methyl ether (hereinafter sometimes abbreviated as MEDG) solvent were mixed at room temperature (25 °C). 59.6 g (0.62 mol) of dimethylpyrazole (hereinafter sometimes abbreviated as DMP, Tokyo Chemical Industry Co., Ltd.) was used as a blocking agent. The mixture was added in several portions so that the temperature of the reaction solution did not exceed 50 °C, and the mixture was stirred for 1 hour. Subsequently, Fourier transform infrared (FT-IR) spectroscopy revealed a peak (2260 cm) derived from the NCO group. -1 The color (near the center) disappeared, confirming that the blockage had been achieved. Next, 21 g of Noigen XL-40 (HLB 10.5, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added, and the mixture was mixed while adding pure water little by little to obtain a crosslinking component dispersion 2 containing 20% ​​by mass of the IPDI trimer-DMP blocked product.

[0235] [Crosslinked component dispersion liquid 3] (Hexamethylene diisocyanate (HDI) nurate blocked with dimethylpyrazole (DMP)) One mole of Duranate TPA-100 (nurate type of hexamethylene diisocyanate, NCO functionality: 3, content: 100% by mass, product name: Asahi Kasei Chemicals Corporation) and methyl isobutyl ketone were added to a reaction vessel and heated to 60 to 70°C. Next, 3 moles of 3,5-dimethylpyrazole were slowly added, and the reaction was continued at 60 to 70°C until the isocyanate content, as confirmed by infrared spectrophotometer, reached zero, thereby obtaining a colorless, transparent, viscous liquid composition containing 98.7% by mass of a dimethylpyrazole-blocked polyisocyanate compound. 180 parts by mass of the composition obtained above, 140 parts by mass of butyl diglycol as an organic solvent, and 20 parts by mass of an ethylene oxide 30 mole adduct of 3-styrenated phenol as a nonionic surfactant were mixed and homogenized. Water was gradually added while stirring, and then the mixture was homogenized at 30 MPa to obtain a crosslinking component dispersion 3 containing 20% ​​by mass of a dimethylpyrazole block compound of hexamethylene diisocyanate nurate.

[0236] [Crosslinked component dispersion 4] (TDI·TMP·MEKO: Dispersion of methyl ethyl ketoxime (MEKO) blocked reaction product of trimethylolpropane (TMP) and toluene diisocyanate (TDI)) First, Polurene AD (product name, manufactured by SAPICI, containing 75% by mass of a reaction product of trimethylolpropane and toluene diisocyanate (2,4 isomer and 2,6 isomer in a mass ratio of 80:20), solvent: ethyl acetate) was prepared as a reaction product of trimethylolpropane and toluene diisocyanate.

[0237] One mole of the reaction product of trimethylolpropane and toluene diisocyanate prepared above was heated to 60 to 70° C. Next, 3 moles of methyl ethyl ketoxime was slowly added, and the mixture was reacted at 60 to 70° C. until the isocyanate content, as confirmed by an infrared spectrophotometer, reached zero. Ethyl acetate was then added, and a colorless, transparent, viscous liquid composition containing 98.7% by mass of a methyl ethyl ketoxime-blocked polyisocyanate compound was obtained.

[0238] 180 parts by mass of the composition obtained above and 20 parts by mass of a nonionic surfactant, an ethylene oxide 30 mole adduct of 3-styrenated phenol, were mixed and homogenized. Water was gradually added while stirring, and the mixture was then homogenized at 30 MPa to obtain a crosslinking component dispersion 4 containing 20% ​​by mass of a methyl ethyl ketoxime-blocked product of the reaction product of trimethylolpropane and toluene diisocyanate.

[0239] <Production of acrylic dispersion> [Materials used] (Acrylic monomer a) Stearyl acrylate: manufactured by Osaka Organic Chemical Industry Co., Ltd. (Acrylic monomer b) Diacetone acrylamide: Tokyo Chemical Industry Co., Ltd. (Acrylic Monomer C) Vinyl chloride: AGC (nonionic surfactants) Noigen XL-100: Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=14.7 (Alkyl-modified silicone) Silwax J1032: Siltech, C32 alkyl dimethicone Silwax L118: Siltech, C18 alkyl dimethicone (cationic surfactant) Stearyltrimethylammonium chloride sulfate: Lion Specialty Chemicals Co., Ltd. (organic solvent) Tripropylene glycol: ADEKA (Polymerization initiator) Azobis(isobutylamidine) dihydrochloride: Fujifilm Wako Pure Chemical Industries, Ltd.

[0240] [Acrylic dispersion 1] An autoclave was charged with 13.6 g of stearyl acrylate, 0.4 g of diacetone acrylamide, 1.0 g of silwax J1032, 1.0 g of silwax L118, 0.8 g of Noigen XL-100, 0.2 g of stearyl trimethylammonium sulfate, 10 g of tripropylene glycol, and 68.8 g of water, and the mixture was stirred at 45° C. This mixture was irradiated with ultrasound to emulsify and disperse all of the monomers. Next, 0.2 g of azobis(isobutylamidine) dihydrochloride was added to the dispersion, and radical polymerization was carried out at 60°C for 6 hours under a nitrogen atmosphere while continuously injecting 4.0 g of vinyl chloride into the autoclave to maintain the internal pressure at 0.3 MPa, to obtain a dispersion containing 20% ​​by mass of acrylic resin.

[0241] <Production of surface treatment agent composition and water- and oil-repellent textile products> The textile products used were 100% undyed polyester (PET) woven fabric, 100% undyed nylon (NY) woven fabric, 100% dyed polyester (PET) woven fabric, and 100% dyed nylon (Ny) woven fabric.

[0242] [Example 1] The silicone dispersion obtained in Production Example 1 was used as a surface treatment agent composition. An undyed 100% polyester (PET) woven fabric and an undyed 100% nylon (Ny) woven fabric were each dipped for 1 second into the treatment liquid so that the silicone dispersion obtained in Production Example 1 was 1% owf. After 1 second, the fabrics were removed and subjected to a heat treatment at 170°C for 1 minute in a high-temperature dryer, yielding a water- and oil-repellent textile product.

[0243] [Examples 2 to 5, Comparative Examples 1 to 3] The same procedure as in Example 1 was carried out, except that the silicone dispersion was as shown in Table 2.

[0244] [Example 6] A surface treatment agent composition was produced by diluting the silicone dispersion obtained in Production Example 6 and the crosslinking component dispersion 1 with pure water so that the silicone dispersion was 5% by mass and the crosslinking component dispersion 1 was 0.5% by mass. Using this surface treatment agent composition as a treatment liquid, a dyed 100% polyester woven fabric and a dyed 100% nylon woven fabric were each dipped in the treatment liquid for 1 second. After 1 second, the fabrics were removed, subjected to a nip treatment (pickup rate 60% by mass), and then dried at 130°C for 1 minute. This was followed by a heat treatment at 170°C for 1 minute to obtain a water- and oil-repellent textile product.

[0245] [Examples 7 to 21, Comparative Examples 4 to 9] The same procedure as in Example 6 was carried out except that the silicone dispersion, acrylic dispersion, and crosslinking component dispersion were as shown in Tables 4 and 5.

[0246] <Evaluation> [Amount of water required to dissolve 1g of organic solvent] For the organic solvent used in each manufacturing example, the amount of water required to dissolve 1 g of the organic solvent was evaluated according to JIS K8001:2017 3.2 "Terminology expressing the degree of solubility," by placing 1 g of the organic solvent in a certain amount of water, shaking vigorously for 30 seconds every 5 minutes at 20°C ± 5°C, and measuring the volume (mL) of water required for dissolution within 30 minutes. Note that in this measurement, 1 mL, 10 mL, 30 mL, 100 mL, or 1000 mL of water was used as the certain amount of water, and it was examined whether 1 g of the organic solvent would dissolve within 30 minutes under the above conditions, and the evaluation criteria were as follows: (Evaluation standard for the amount of water required to dissolve 1g of organic solvent) Less than 1 mL: Dissolved in 1 mL of water within 30 minutes. More than 1 mL and less than 10 mL: Did not dissolve in 1 mL of water within 30 minutes, but dissolved in 10 mL of water within 30 minutes. More than 10 mL but not more than 30 mL: Did not dissolve in 10 mL of water within 30 minutes, but dissolved in 30 mL of water within 30 minutes. More than 30 mL but not more than 100 mL: Did not dissolve in 30 mL of water within 30 minutes, but dissolved in 100 mL of water within 30 minutes. Over 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. Over 1000mL: Did not dissolve in 1000mL of water within 30 minutes.

[0247] [Product stability of surface treatment composition] The product stability of the surface treatment composition was evaluated by centrifugation. 100 g of the surface treatment composition was weighed into a 1 L centrifuge bottle, the bottle was capped, and centrifuged at 20°C, 8000 rpm, and 30 minutes. The supernatant after centrifugation was transferred to a separate container and its mass was weighed. The sedimentation rate was calculated according to the following formula. Sedimentation rate (%) = {(mass of surface treatment composition weighed in centrifuge bottle) - (mass of supernatant)} / 100 The lower the settling rate, the better the product stability.

[0248] [Processing stability of surface treatment composition] The processing stability of the surface treatment composition was evaluated by a homomixer test. The surface treatment composition was diluted to 5% by mass with purified water and stirred at 5,000 rpm for 10 minutes at room temperature (25°C) using a homomixer (manufactured by Primix Corporation, model number: TK Robomix D162 Homomixer MARK II), followed by standing for 10 minutes. The mixture was filtered through a black cotton cloth, and the condition of the black cotton cloth was evaluated on a 5-point scale. 5: No precipitates at all 4: Slight deposits observed 3: Precipitation is observed along the holes of the Buchner funnel 2: Precipitation is observed covering the entire surface of the cotton fabric. 1: The entire surface of the cotton cloth is covered with deposits.

[0249] [Initial water repellency of water- and oil-repellent textile products] The water repellency test was conducted in accordance with the spray method of JIS L 1092 (2009) 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 added to the grade, and if the characteristics were between grades 4 and 5, the grade was assigned a "4-5". The evaluation criteria for water repellency are as follows: Water repellency: Condition 5: No adhesion or wetness on the surface 4: Slight adhesion and wetting on the surface 3: Shows partial surface wetting 2: Surface wetness 1: Shows wetting of the entire surface 0: Both sides are completely wet

[0250] [Durable water repellency for water- and oil-repellent textile products] The water- and oil-repellent textile product was washed 10 times (L-10) according to the 103 method of JIS L 0217 (1995), and the water repellency after air drying was evaluated in the same manner as in the water repellency evaluation method described above.

[0251] [Texture of water- and oil-repellent textile products] The water-repellent and oil-repellent textile products were evaluated by handling according to the following five-point scale. 1: Hard ~ 5: Soft

[0252] [Peel strength] Hot melt adhesive tape (manufactured by Sun Chemical Industry Co., Ltd., product number: BW-II) was adhered to the textile products obtained in the Examples and Comparative Examples using a scorch tester (manufactured by Todoroki Industries Co., Ltd., model number: UST-2ASL) at 130°C for 20 seconds. The peel strength [N / 25mm width] was measured using an autograph (manufactured by Shimadzu Corporation; AG-IS MO type) in a constant temperature and humidity room environment of 20°C and 65% RH in accordance with JIS L 1086:2013 7.10.1. The peel strength was the average value of three test pieces. The higher the value, the better the result.

[0253] [Seam slip resistance (slip resistance)] The textile products obtained in the examples and comparative examples were measured in accordance with JIS L1096:2010 seam slippage method B. The smaller the value, the better the result. Measurement procedure 1. Using an autograph (Shimadzu Corporation; AG-IS MO type), the specimen was 100% nylon fabric, with a grip distance of 76.2 mm and a pulling speed of 300 cm / min. A load of 117.7 N (12 kgf) was applied. 2. After removing the test piece from the autograph and leaving it for 1 hour, a load was applied perpendicular to the seam (pulled with a finger) to the extent that the slack around the seam disappeared, and the size of the largest hole in the seam slippage was measured to the nearest 0.1 mm and expressed as an average value (to one decimal place).

[0254] [Table 1]

[0255] [Table 2]

[0256] [Table 3]

[0257] [Table 4]

[0258] [Table 5]

[0259] It was confirmed that the water- and oil-repellent textile products treated with the surface treatment agents of Examples 1 to 21 were excellent in durable water repellency and peel resistance. [Industrial Applicability]

[0260] The surface treatment agent composition of the present invention has excellent durable water repellency and peeling resistance, and is useful for producing water- and oil-repellent products such as water- and oil-repellent textile products.

Claims

1. The composition comprises a silicone resin (A) and an organopolysiloxane (B) containing a silanol group, The silicone resin (A) contains MQ, MDQ, MTQ and MDTQ as components {M, D, T and Q are each (R″) 3 SiO 0.5 Units, (R'') 2 SiO unit, R″SiO 1.5 Units and SiO 2 represents a unit, and R″ represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms. Surface treatment composition.

2. The silanol group-containing organopolysiloxane (B) is represented by the following formula (1): 【Chemistry 1】 [In formula (1), X is an OH group or a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms which may have a substituent; n is a real number greater than or equal to 1, R is an OH group or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent. It has a structure represented by The surface treatment composition according to claim 1.

3. The surface treatment composition according to claim 1 , further comprising an alkylpolysiloxane.

4. The surface treatment agent composition according to claim 1 , further comprising a polyfunctional isocyanate.

5. The surface treatment agent composition according to claim 1 , further comprising a hydrophobic organic solvent.

6. A water- and oil-repellent textile product obtained by treating the textile product with the surface treatment composition according to any one of claims 1 to 5.

7. A method for producing a water- and oil-repellent textile product, comprising a step of treating the textile product with a treatment liquid containing the surface treatment agent composition according to any one of claims 1 to 5.

8. A method for producing the surface treatment agent composition according to claim 3, comprising: A method comprising mixing a silicone resin (A), an organopolysiloxane (B) containing silanol groups, and an alkylpolysiloxane.

9. A method for producing the surface treatment agent composition according to claim 5, comprising: A method comprising mixing a silicone resin (A), an organopolysiloxane containing silanol groups (B), and a hydrophobic organic solvent.

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