Water-repellent oil-repellent agent composition, water-repellent oil-repellent fiber product, and method for producing same

Abstract

Provided are: a water-repellent and oil-repellent agent composition which uses a silicone-based compound having excellent water-repellent and oil-repellent properties and which has excellent product stability (more specifically, long-term storage stability) and excellent processing stability; a water-repellent and oil-repellent fiber product; and a method for producing the water-repellent and oil-repellent fiber product. In one aspect, provided is a water-and oil-repellent agent composition comprising a silicone resin, an organic solvent, an emulsifier, and an aqueous medium, the organic solvent being an organic solvent in which the amount of water required to dissolve 1 g of the organic solvent at 20 DEG C exceeds 10 mL.

Description

Technical Field

[0001] The present invention relates to a water- and oil-repellent composition, a water- and oil-repellent fiber product and a method for producing the same. Background Art

[0002] In the past, it was known that the fluorine-based water- and oil-repellent agent with fluorine-based and by processing fiber products etc. with such fluorine-based water- and oil-repellent agent, thereby giving water and oil repellency to the fiber products of surface.Such fluorine-based water- and oil-repellent agent is generally manufactured by making the monomer (monomer) with fluoroalkyl group carry out homopolymerization or copolymerization.Although the fiber products processed with fluorine-based water- and oil-repellent agent have brought into play excellent water and oil repellency, the monomer with fluoroalkyl group is difficult to decompose, and therefore has problems in terms of environment.

[0003] Therefore, in recent years, non-fluorine-containing water repellents that do not contain fluorine have been studied. For example, in the following patent document 1, a water repellent consisting of a specific non-fluorine-containing polymer of a (meth) acrylic ester containing an ester moiety with a carbon number of 12 or more as a monomer unit is described. In addition, in the following patent document 2, a water repellent composition for fibers is described, which is a water repellent composition comprising component (A), a silicone resin (B) and water, wherein the component (A) is selected from at least one of a carbamate compound (A1) having at least one hydrocarbon having 12 or more carbon atoms in the molecule, an acrylic resin (A2) having at least one hydrocarbon having 12 or more carbon atoms in the molecule, and a reactive silicone (A3), wherein the carbamate compound (A1) and the acrylic resin (A2) have at least one hydrocarbon having at least one carbon number of 12 or more in the molecule, and the unit constituting the silicone resin (B) is selected from R3SiO 1 / 2 The M unit shown, SiO 4 / 2 Q unit and RSiO shown 3 / 2 At least one of the T units shown (excluding only M units and only Q units), wherein the above-mentioned R represents a linear or branched monovalent alkyl group having 1 to 18 carbon atoms.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2006-328624

[0007] Patent Document 2: Japanese Patent Application Publication No. 2019-173185 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] Silicone compounds are useful as water- and oil-repellent components because they are fluorine-free and have excellent water and oil repellency. Furthermore, the technology described in Patent Document 2 aims to provide a fiber water repellent composition that exhibits low slippage when attached to fiber products, etc., by using a specific silicone compound as a water-repellent component. However, conventional silicone water repellent compositions have suffered from insufficient product stability and processing stability.

[0010] The object of the present invention is to solve the above-mentioned problems and provide a water- and oil-repellent composition using an organosilicon compound having excellent water- and oil-repellency and excellent product stability (more specifically, long-term storage stability) and processing stability, as well as a water- and oil-repellent fiber product and a method for producing the same.

[0011] Means for solving problems

[0012] The present disclosure includes the following items.

[0013] [1] A water- and oil-repellent composition comprising a silicone resin, an organic solvent, an emulsifier, and an aqueous medium.

[0014] The organic solvent is an organic solvent in which the amount of water required to dissolve 1 g of the organic solvent at 20° C. exceeds 10 mL.

[0015] [2] The water- and oil-repellent composition according to item 1, further comprising an amino-modified silicone.

[0016] [3] The water- and oil-repellent composition according to item 1 or 2, further comprising an alkyl polysiloxane.

[0017] [4] The water- and oil-repellent composition according to any one of items 1 to 3, further comprising a polyfunctional isocyanate.

[0018] [5] A water- and oil-repellent fiber product obtained by treating the fiber product with the water- and oil-repellent composition according to any one of items 1 to 4.

[0019] [6] A method for producing a water- and oil-repellent fiber product, comprising treating the fiber product with a treatment liquid containing the water- and oil-repellent composition according to any one of items 1 to 4.

[0020] Effects of the Invention

[0021] According to one embodiment of the present invention, a water- and oil-repellent composition using an organosilicon compound having excellent water- and oil-repellency and excellent product stability (more specifically, long-term storage stability) and processing stability, as well as a water- and oil-repellent fiber product and a method for producing the same can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a graph showing the evaluation results of the processing stability of the water- and oil-repellent composition. DETAILED DESCRIPTION

[0023] Hereinafter, a preferred embodiment of the present invention (hereinafter also referred to as the present embodiment) will be described in detail. However, the present invention is not limited to the following embodiment.

[0024] Water and oil repellent composition

[0025] The water- and oil-repellent composition of the present embodiment comprises a silicone resin, an organic solvent, an emulsifier, and an aqueous medium, wherein the organic solvent is an organic solvent in which the amount of water required to dissolve 1g of the organic solvent exceeds 10mL at 20°C. The water- and oil-repellent composition of the present embodiment has excellent water and oil repellency, and good product stability and processing stability. In one embodiment, the seam slippage of the water- and oil-repellent composition of the present embodiment can also be good.

[0026] In addition, the organic solvent mentioned in the present disclosure can be liquid at 25°C.

[0027] Hereinafter, suitable examples of each component will be described.

[0028] Silicone resin

[0029] In one embodiment, the silicone resin comprises MQ, MDQ, MT, MTQ, MDT, or MDTQ as a constituent component. The silicone resin is preferably solid at 25°C and is preferably an organopolysiloxane having a three-dimensional structure. Furthermore, the silicone resin preferably has a hardness of 20 or greater, more preferably 60 or greater, as measured by a type A durometer in accordance with JIS K 6249:2003, Section 13. Hardness test. Here, M, D, T, and Q each represent (R")3SiO 0.5 unit, (R”)2SiO unit, R”SiO 1.5 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.

[0030] In one aspect, silicone resins are generally known as MQ resins, MT resins, or MDT resins, and sometimes have moieties represented as MDQ, MTQ, or MDTQ.

[0031] Silicone resin can also be obtained as a solution of a suitable solvent dissolved in alkylpolysiloxane or in addition to the alkylpolysiloxane. As the solvent in addition to the alkylpolysiloxane, for example, n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane and a mixture of these solvents can be enumerated. The above-mentioned alkylpolysiloxane as a solvent can constitute the alkylpolysiloxane described later that the water- and oil-repellent composition of the present embodiment can include.

[0032] Examples of solutions in which a silicone resin is dissolved in an alkyl polysiloxane include KF7312J (a mixture of trimethylsilyl-containing polysiloxane and decamethylcyclopentasiloxane in a ratio of 50:50), KF7312F (a mixture of trimethylsilyl-containing polysiloxane and octamethylcyclotetrasiloxane in a ratio of 50:50), KF9021L (a mixture of trimethylsilyl-containing polysiloxane and low-viscosity methyl polysiloxane in a ratio of 50:50), and KF7312L (a mixture of trimethylsilyl-containing polysiloxane and low-viscosity methyl polysiloxane in a ratio of 50:50), all of which are commercially available from Shin-Etsu Chemical Co., Ltd.

[0033] Examples of the single silicone resin include MQ-1600 solid resin (trimethylsilyl group-containing polysiloxane) and MQ-1640 flake resin (trimethylsilyl group-containing polysiloxane, polypropylsilsesquioxane) commercially available from Torayada Co., Ltd. These commercially available products contain trimethylsilyl group-containing polysiloxane and include MQ, MDQ, MT, MTQ, MDT, or MDTQ.

[0034] Organic solvents

[0035] The water- and oil-repellent composition of the present embodiment is included in an organic solvent in which the amount of water required to dissolve 1g of organic solvent at 20°C exceeds 10mL. In one embodiment, the amount of water required to dissolve 1g of organic solvent exceeds 30mL, preferably exceeds 100mL, and more preferably exceeds 1000mL. Such an organic solvent contributes to the formation of an emulsion dispersion formed by stably emulsifying and dispersing the silicone resin, and therefore contributes to the formation of a water- and oil-repellent composition with excellent product stability and processing stability. In the present disclosure, the so-called emulsified dispersion or emulsified dispersion refers to a liquid medium in which the liquid exists in an emulsified state and / or the solid exists in a dispersed state. In one embodiment, it can be considered that the organic solvent in which the amount of water required to dissolve 1g of organic solvent at 20°C exceeds 10mL contributes to improving the water- and oil-repellent property by improving the film-forming property of the silicone compound as a water- and oil-repellent component on the fiber. The amount of water required to dissolve 1 g of the organic solvent is a value measured according to JIS K8001:2017 by the method described in the section "Examples" of the present disclosure.

[0036] Although not bound by theory, it is speculated that when the silicone resin is emulsified and dispersed in a medium containing water to form an emulsified dispersion or a water- and oil-repellent composition, the organic solvent of the present embodiment contributes to the improvement of the emulsified dispersion stability of the silicone resin in the medium containing water by promoting the O / W type emulsified dispersion of the silicone resin.

[0037] In order to effectively improve the emulsified dispersion stability of the silicone resin, the organic solvent preferably has a structure composed of carbon and hydrogen (ie, a hydrocarbon structure) in its molecule, in which the amount of water required to dissolve 1 g of the organic solvent at 20°C exceeds 10 mL. From this viewpoint, preferred organic solvents include esters (specific examples include 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, ethyl acetate, butyl acetate, butanediol 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, ethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, etc.), alcohols (specific examples include 1-butanol, 1-pentanol, isooctyl alcohol, etc.), aromatic solvents (specific examples include toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), and petroleum solvents (specific examples include isoparaffins, mineral oil, mineral spirits, synthetic oils such as poly-α-olefins, etc.). These organic solvents can be used alone or in combination of two or more.

[0038] The isoparaffin preferably has 4 or more carbon atoms, more preferably 9 to 20 carbon atoms.

[0039] Examples of such isoparaffins include IP solvent IP-2028 (isoparaffin having 10 to 16 carbon atoms, manufactured by Idemitsu Kosan Co., Ltd.).

[0040] Examples of mineral oil include those with a kinematic viscosity of 50 mm at 30°C. 2 / s or less mineral oil, more specifically, n-undecane, n-dodecane, n-tridecane, n-tetradecane, paraffin, etc. can be mentioned. It should be noted that the above-mentioned kinematic viscosity is a value measured by a method according to JIS K 2283:2000. The number of carbon atoms of paraffin can be, for example, 10 to 16. Mineral oil can be used alone or in combination of two or more. In the case of a combination of two or more, they are preferably compatible with each other. Mineral oil can be a commercially available product, and examples thereof include, for example, Kakutasu noru maru paraffin N-12D, Kakutasu noru maru paraffin YHNP, Kakutasu noru maru paraffin N-14 (all of which can be obtained from ENEOS Co., Ltd.), etc.

[0041] As mineral spirits, those having a boiling point of 130 to 230°C are particularly preferred.

[0042] The amount of the organic solvent in the water- and oil-repellent composition, in which the amount of water required to dissolve 1 g of the organic solvent exceeds 10 mL at 20° C., is preferably 10 to 500 parts by mass, more preferably 20 to 400 parts by mass, and still more preferably 30 to 300 parts by mass, relative to 100 parts by mass of the silicone resin. In terms of the product stability and processing stability of the water- and oil-repellent composition over time, the amount of the organic solvent is preferably within the above range.

[0043] Emulsifier

[0044] In one embodiment, emulsifying agent can be surfactant.Surfactant can include more than one surfactant selected from cationic surfactant, anionic surfactant, nonionic surfactant and amphoteric surfactant.From the viewpoint that the emulsion stability and water and oil repellency of the water and oil repellent composition can be made good, surfactant is preferably nonionic surfactant and / or cationic surfactant, more preferably the combination of nonionic surfactant and cationic surfactant.In one embodiment, surfactant preferably does not include anionic surfactant.

[0045] [Nonionic surfactant]

[0046] Examples of the nonionic surfactant include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0047] Examples of the ether include compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0048] Examples of the ester include esters of alcohols and fatty acids.

[0049] Examples of the ester ether include compounds obtained by adding an alkylene oxide such as ethylene oxide to an ester of an alcohol and a fatty acid.

[0050] In the above-mentioned esters or ester ethers, the alcohol includes 1-6 valence, preferably 2-5 valence, alcohols having 1 to 50 carbon atoms, preferably 3 to 30 carbon atoms. The alcohol is preferably an aliphatic alcohol. In the above-mentioned esters or ester ethers, the fatty acid includes saturated or unsaturated fatty acids having 2 to 50 carbon atoms, preferably 5 to 30 carbon atoms.

[0051] Alkanolamides can be formed from fatty acids and alkanolamines. The alkanolamides can be, for example, monoalkanolamides or dialkanolamides. The fatty acids can be saturated or unsaturated fatty acids having 2 to 50 carbon atoms, preferably 5 to 30 carbon atoms. The alkanolamines can be, for example, alkanols 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.

[0052] Examples of the polyol include di- to pentavalent alcohols having 15 to 30 carbon atoms.

[0053] The amine oxide may be an amine oxide. The amine may be a secondary amine or a tertiary amine. The amine oxide preferably has 5 to 50 carbon atoms.

[0054] 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.

[0055] More specific suitable examples of nonionic surfactants include linear and / or branched saturated and / or unsaturated aliphatic group alkylene oxide adducts, linear and / or branched saturated and / or unsaturated fatty acid polyalkylene glycol esters, polyoxyethylene (POE) / polyoxypropylene (POP) random or block copolymers, acetylene glycol alkylene oxide adducts, etc. The structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is preferably polyoxyethylene (POE) or polyoxypropylene (POP), or a POE / POP random or block copolymer.

[0056] From the viewpoint of biodegradability, environmental hormone effects, and other environmental loads, the nonionic surfactant preferably does not contain an aromatic structure.

[0057] In a preferred embodiment, the nonionic surfactant is a compound represented by the following formula (1).

[0058] R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 (1)

[0059] [Where,

[0060] 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,

[0061] R 2 When there are multiple groups, each group independently represents an alkylene group having 3 or more carbon atoms.

[0062] 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,

[0063] p is a number greater than 2, and

[0064] q is a number greater than or equal to 0 or 1.]

[0065] R 1 The number of carbon atoms in R is preferably 8 to 20, more preferably 10 to 18. 1 Preferred are lauryl, tridecyl or oleyl.

[0066] R 2 An alkylene group having 3 to 10 carbon atoms is preferred, and a propylene group or a butylene group is more preferred.

[0067] p is preferably 3 or more or 5 or more, and is preferably 200 or less.

[0068] 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.

[0069] 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, but among these, an oxypropylene moiety is preferred.

[0070] In a preferred embodiment, the nonionic surfactant is a compound represented by the following formula (2).

[0071] R 1 O-(CH2CH2O) p -H(2)

[0072] [Where R 1 and p are the same as those defined in formula (1).]

[0073] In a preferred embodiment, the nonionic surfactant is a compound represented by any one of the following formula group (3).

[0074] C 10 H 21 O-(CH2CH2O) p -(C3H6O) q -H

[0075] C 12 H 25 O-(CH2CH2O) p -(C3H6O) q -H

[0076] C 15 H 31 O-(CH2CH2O) p -(C3H6O) q -H

[0077] C 16 H 33 O-(CH2CH2O) p -(C3H6O) q -H

[0078] C 17 H 35 O-(CH2CH2O) p -(C3H6O) q -H

[0079] C 18 H 37 O-(CH2CH2O) p -(C3H6O) q -H

[0080] C 12 H 25 O-(CH2CH2O) p -(C3H6O) q -C 12 H 25

[0081] C 15 H 31 O-(CH2CH2O) p -(C3H6O) q -C 15 H 31

[0082] C 16 H 33 O-(CH2CH2O) p -(C3H6O) q -C 12 H 25

[0083] iso-C 13 H 27 O-(CH2CH2O) p -(C3H6O) q -H

[0084] C 10 H 21 COO-(CH2CH2O) p -(C3H6O) q -H

[0085] C 16 H 33 COO-(CH2CH2O) p -(C3H6O) q -C 12 H 25 (3)

[0086] [In the formula, p and q are the same as those defined in formula (1).]

[0087] More specific examples of nonionic surfactants include ethylene oxide and hexylphenol, isooctamethylphenol, hexadecanol, oleic acid, paraffin (C 12 -C 16 ) thiol, sorbitan monofatty acid (C7-C 19 ) ester or alkyl (C 12 -C 18 ) condensation products of amines, etc.

[0088] When the nonionic surfactant has a polyoxyethylene block, in one embodiment, the mass ratio of the polyoxyethylene block in the molecule may be 5 to 80 mass %, 30 to 75 mass %, or 40 to 70 mass %.

[0089] The nonionic surfactant may be a single species or a combination of two or more species, but is preferably a combination of two or more species. In the combination of two or more species, it is preferred that at least one nonionic surfactant is R in the above formula (1) or (2). 1 Base and / or R 3 The alkyl group or the alkyl group in the above formula (3) 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 the total of 100 mass % of the nonionic surfactants that can be more than two kinds. In the combination of more than two nonionic surfactants, at least one nonionic surfactant can be a compound other than the above branched compound. As such a compound, R in the above formula (1) or (2) can be cited. 1 Base and / or R 3 The compound wherein the alkyl group or the alkyl group in the above formula (3) is a saturated or unsaturated straight-chain alkyl group such as lauryl.

[0090] As the particularly suitable example of nonionic surfactant, can enumerate polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerol fatty acid ester, polyoxyethylene glycerol fatty acid ester, polyglycerol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkanolamide, alkyl alkanolamide, acetylenic alcohol (such as acetylenic glycol), the oxyethylene adduct of acetylenic glycol, polyethylene glycol polypropylene glycol block copolymer etc..From by reducing the dynamic surface tension of water and oil repellent composition thereby being easy to making said composition penetrate into the viewpoint of fiber product, as nonionic surfactant, be preferably the oxyethylene adduct of acetylenic alcohol (such as acetylenic glycol) or this acetylenic alcohol.

[0091] In a preferred embodiment, the nonionic surfactant is an alcohol having an unsaturated triple bond or an oxyalkylene adduct of the alcohol (hereinafter 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 monohydric alcohol or a polyhydric alcohol. The oxyalkylene adduct structure preferably comprises a polyoxyalkylene adduct structure, such as a polyoxyethylene adduct structure, a polyoxypropylene adduct structure, or a random or block adduct structure of polyoxyethylene and polyoxypropylene.

[0092] The triple bond alcohol compound may be a compound represented by the following formula (4) or (5) or an alkylene oxide adduct thereof. The number of carbon atoms of the alkylene oxide is preferably 1 to 20 or 2 to 5, and suitable examples of the alkylene oxide are ethylene oxide or propylene oxide. The number of alkylene oxide additions is preferably 1 to 50. The alkyl group in the following formula (4) or (5) is preferably a linear or branched alkyl group having 1 to 12 or 1 to 6 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, butyl group, or isobutyl group.

[0093] HO-CR 11 R 12 -C≡C-CR 13 R 14 -OH(4)

[0094] [Where R 11 、R 12 、R 13 and R 14 Each independently represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.]

[0095] HO-CR 15 R 16 -C≡CH(5)

[0096] [Where R 15 and R 16 Each independently represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.]

[0097] Specific examples of triple bond alcohol compounds include acetylene glycols, propargyl alcohol, 2,5-dimethyl-3-hexyn-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-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-hexyn-2,5-diol, 2-butyn-1,4-diol, and the like, as well as polyethoxylates and ethylene oxide adducts thereof.

[0098] The nonionic surfactant may be one or both of a compound having a triple bond and a compound not having a triple bond. In the combination of a compound having a triple bond and a compound not having a triple bond, in one embodiment, 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.

[0099] In one embodiment, the weight average molecular weight of the nonionic surfactant may be 300 to 5,000 or 500 to 3,000. The weight average molecular weight is a value measured using gel permeation chromatography (GPC) with polyethylene glycol as a standard.

[0100] [Cationic surfactant]

[0101] Examples of cationic surfactants include amines, amine salts, quaternary ammonium salts, imidazolines, and imidazolines. In one embodiment, the cationic surfactant does not have an amide group. Suitable examples of cationic surfactants are amine salts, quaternary ammonium salts, and ethylene oxide addition type ammonium salts. Specific examples of cationic surfactants include alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridine Salt, alkylisoquinoline Quaternary ammonium surfactants such as benzethonium chloride, etc.

[0102] In a preferred embodiment, the cationic surfactant is a compound represented by the following formula (6). The hydrocarbon group in the formula may have an oxygen atom, for example, it may be an oxyalkylene group such as a polyoxyalkylene group. The number of carbon atoms in the alkylene portion is, for example, 2 to 5. 21 、R 22 、R 23 or R 24 The hydrocarbon group may be an aliphatic, aromatic or a combination thereof. 21 、R 22 、R23 and R 24 Each independently is preferably a hydrocarbon group having 1 to 30 carbon atoms.

[0103] R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - (6)

[0104] [Where,

[0105] 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,

[0106] X represents an anionic group.]

[0107] R 21 、R 22 、R 23 and R 24 Specific examples of are alkyl groups (eg, methyl, butyl, stearyl, and palmityl), aryl groups (eg, phenyl), aralkyl groups (eg, benzyl and phenethyl), and the like.

[0108] Specific examples of X include halogens and acids. Halogens may be, for example, chlorine. Acids may be inorganic acids such as hydrochloric acid or organic acids such as acetic acid (particularly fatty acids).

[0109] In a preferred embodiment, the cationic surfactant is a monoalkyltrimethylammonium salt, and the number of carbon atoms in the alkyl portion can be, for example, 4 to 30.

[0110] In a preferred embodiment, the cationic surfactant is an ammonium salt, particularly a quaternary ammonium salt. The cationic surfactant may be an ammonium salt represented by the following formula (7).

[0111] R 31 p -N + R 32 q X - (7)

[0112] [Where,

[0113] R 31 When there are multiple groups, each group independently represents a linear or branched saturated or unsaturated aliphatic group having 12 or more carbon atoms.

[0114] R 32When there are multiple groups, each group independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a benzyl group, or a polyoxyethylene group.

[0115] X represents a halogen atom or a fatty acid salt group having 1 to 4 carbon atoms,

[0116] p is 1 or 2,

[0117] q is 2 or 3, where p+q=4.]

[0118] R 31 The number of carbon atoms in the alkyl group is preferably 12 to 50 or 12 to 30.

[0119] In R 32 In the polyoxyethylene group, in one embodiment, the number of repetitions of the oxyethylene unit may be 1 to 50, 2 to 50, or 3 to 50, and is preferably 1 or 2.

[0120] X is preferably chlorine or bromine.

[0121] Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydrogen polyoxyethylene)ammonium chloride, and benzyldodecyldi(hydrogen polyoxyethylene)ammonium chloride.

[0122] [Amphoteric surfactants]

[0123] Examples of amphoteric surfactants include alanine, imidazoline Betaines, amidobetaines, betaine acetate, etc., specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline Betaine, lauryl dimethylaminoacetic acid betaine, fatty acid amide propyl dimethylaminoacetic acid betaine, etc.

[0124] In one embodiment, the surfactant may be a combination of one or more nonionic surfactants, one or more cationic surfactants, and one or more amphoteric surfactants.

[0125] In one embodiment, the amount of the cationic surfactant is preferably 15% by mass or more, more preferably 20% by mass or more, and particularly preferably 25% by mass or more, relative to the total amount of surfactants (100% by mass). When a combination of a nonionic surfactant and a cationic surfactant is used, the mass ratio of the nonionic surfactant to the cationic surfactant is preferably 85:15 to 20:80, more preferably 80:20 to 40:60.

[0126] The amount of the cationic surfactant can 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.

[0127] The total amount of the emulsifier, particularly the surfactant, can 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.

[0128] The HLB of the nonionic surfactant is preferably 6-15, 6.5-14, 7-13, or 8-12 from the viewpoint of product stability of the water- and oil-repellent composition.

[0129] In addition, the "HLB" in this disclosure is calculated based on Griffey's HLB. Here, the hydrophilic group refers to an oxyethylene group.

[0130] HLB = (hydrophilic group × 20) / molecular weight

[0131] HLB of nonionic surfactant = (molecular weight of the hydrophilic group of the nonionic surfactant) × 20 / molecular weight of the nonionic surfactant

[0132] <Aqueous medium>

[0133] The water- and oil-repellent composition of the present embodiment further includes an aqueous medium different from the organic solvent of the present embodiment (that is, an organic solvent in which the amount of water required to dissolve 1g of organic solvent exceeds 10mL at 20°C). In one embodiment, the aqueous medium is an organic solvent in which the amount of water required to dissolve 1g of organic solvent is less than 10mL at 20°C, as evaluated by the method described in the item of [Examples] of the present disclosure. In one embodiment, the aqueous medium is an alcohol. Alcohol can be used alone or in combination of two or more. As alcohol, there is no particular limitation, and for example, alcohols having 1 to 6 carbon atoms can be cited, preferably methanol, ethanol, isopropyl alcohol, glycerol, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, glycerol, butylene glycol, butyl diglycol, and solfate can be cited. In addition, compounds other than alcohols such as N-methylpyrrolidone, dimethylformamide, and dimethyl sulfoxide can also be mentioned. These organic solvents are miscible with water and can be contained in the water- and oil-repellent composition as a mixed solvent with water.

[0134] <Amino-modified silicone>

[0135] In one embodiment, the water- and oil-repellent composition may further include amino-modified silicone. Amino-modified silicone is advantageous as a water-repellent component. Examples of amino-modified silicone include compounds having an organic group containing an amino group and / or an imino group on the side chain or at the end of an organopolysiloxane. Examples of such organic groups include organic groups represented by -R-NH2 and organic groups represented by -R-NH-R'-NH2. Examples of R and R' include divalent groups such as ethylene and propylene. Part or all of the amino and / or imino groups may be blocked amino and / or imino groups. Blocked amino and / or imino groups may be obtained, for example, by treating the amino and / or imino groups with a blocking agent. Examples of blocking agents include fatty acids having 2 to 22 carbon atoms, anhydrides of fatty acids having 2 to 22 carbon atoms, acyl halides of fatty acids having 2 to 22 carbon atoms, and aliphatic monoisocyanates having 1 to 22 carbon atoms. In addition, in this disclosure, the organic group refers to a group having 1 or more carbon atoms.

[0136] From the viewpoints of water repellency, durable water repellency, hand feel, and seam slippage, the functional group equivalent weight of the amino-modified silicone is preferably 100 to 20,000 g / mol, more preferably 150 to 12,000 g / mol, and even more preferably 200 to 4,000 g / mol.

[0137] The amino-modified silicone is preferably liquid at 25° C. The kinematic viscosity of the amino-modified silicone at 25° C. is preferably 10 to 100,000 mm 2 / s, more preferably 10 to 30,000 mm 2 / s, more preferably 10 to 5,000 mm 2 / s. The kinematic viscosity at 25°C is 100,000 mm 2 When the viscosity is 0.05 μm or less, workability and joint slippage properties tend to be easily ensured. The kinematic viscosity at 25° C. refers to a value measured by the method described in JIS K 2283:2000 (Ubbelohde viscometer).

[0138] As amino-modified silicone, commercially available products can be used. Examples of commercially available products include KF8005, KF-868, KF-864, and KF-393 (all manufactured by Shin-Etsu Chemical Co., Ltd.), XF42-B1989 (manufactured by Momentibu Parffold Materials Diapan Co., Ltd.), and SF-8417 and BY16-853U (all manufactured by Toray Dawu Coning Co., Ltd.).

[0139] The amino-modified silicone may be used alone or in combination of two or more.

[0140] The amino and / or imino groups of amino-modified silicone may be partially or completely neutralized, or may be unneutralized. Neutralization can be performed using organic acids such as lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, methanesulfonic acid, and toluenesulfonic acid; or inorganic acids such as hydrogen chloride, sulfuric acid, and nitric acid.

[0141] When making the water- and oil-repellent composition be a treatment bath (for example, the treatment bath to which fiber is treated), the compounding amount of the amino-modified silicone in the water- and oil-repellent composition of the present embodiment can be 0.01 to 1% by mass based on the water- and oil-repellent composition total amount. In addition, when circulating, the compounding amount of the amino-modified silicone can be 0.1 to 50% by mass based on the water- and oil-repellent composition total amount, or 0.2 to 20% by mass.

[0142] From the viewpoints of water repellency, feel, and seam slippage, the water- and oil-repellent composition of the present embodiment, when containing amino-modified silicone, may contain a silicone resin in an amount of 50 to 15,000 parts by mass, 100 to 10,000 parts by mass, 150 to 6,000 parts by mass, 500 to 15,000 parts by mass, or 900 to 6,000 parts by mass relative to 100 parts by mass of the amino-modified silicone.

[0143] <Alkyl polysiloxane>

[0144] In one embodiment, the water and oil repellent composition can further include alkyl polysiloxane.Alkyl polysiloxane is advantageous as a water repellent component.Alkyl polysiloxane is a compound having a saturated hydrocarbon group in the side chain and terminal of a chain organopolysiloxane or a saturated hydrocarbon group in the side chain of a cyclic organopolysiloxane. As alkyl polysiloxane, for example, the compound shown in the following general formula (8), the compound shown in the following general formula (9) etc. can be enumerated.

[0145]

[0146] [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 an integer greater than 1.]

[0147]

[0148] [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 an integer of 2 to 20.]

[0149] 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 Each is independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms. From the viewpoint that the silicone resin is easily soluble in the compound represented by the general formula (8) and the compound is easily obtained, the number of carbon atoms of the saturated hydrocarbon group is preferably 1 to 10. The saturated hydrocarbon group may be linear or branched. The saturated hydrocarbon group is preferably linear, more preferably a linear alkyl group. The saturated hydrocarbon group is preferably methyl or ethyl, more preferably a methyl group. v is an integer greater than 1. v can be appropriately selected in such a way that the kinematic viscosity of the compound represented by the general formula (8) is within the range of the kinematic viscosity of the alkyl polysiloxane described below. In one embodiment, it can be 0.1 to 100,000 mm 2 / s.

[0150] Examples of the compound represented by the general formula (8) include dimethylpolysiloxane and diethylpolysiloxane.

[0151] In the compound represented by the general formula (9) used in this embodiment, R 19 and R 20 Each is independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms. The number of carbon atoms of the saturated hydrocarbon group is preferably 1 to 10. When the number of carbon atoms of the saturated hydrocarbon group is within the above range, there is a tendency that the silicone resin is easily dissolved in the compound represented by the general formula (9), and the compound is easily obtained. The saturated hydrocarbon group can be linear or branched. The saturated hydrocarbon group is preferably linear, and more preferably a linear alkyl group. The saturated hydrocarbon group is preferably methyl or ethyl, and more preferably a methyl group. w is an integer of 2 to 20. w is preferably 3 to 10, and more preferably 4 or 5. When w is within the above range, there is a tendency that the silicone resin is easily dissolved in the compound represented by the general formula (9), and the compound is easily obtained.

[0152] Examples of the compound represented by the general formula (9) include decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane.

[0153] The alkyl polysiloxanes can be used alone or in combination of two or more.

[0154] The alkyl polysiloxane is preferably liquid at 25° C. The kinematic viscosity of the alkyl polysiloxane at 25° C. is preferably 0.1 to 100,000 mm 2 / s, more preferably 0.1 to 10,000 mm 2 / s, more preferably 0.1 to 1,000 mm 2 / s, more preferably 0.1 to 500 mm 2 / s, particularly preferably 0.1 to 100 mm 2 When the kinematic viscosity at 25°C is within the above range, the silicone resin tends to dissolve easily in the alkyl polysiloxane, making it easier to ensure workability. The kinematic viscosity at 25°C refers to the value measured by the method described in JIS K 2283:2000 (Ubbelohde viscometer).

[0155] From the viewpoint of water repellency, hand feel, and seam slippage, the amount of alkyl polysiloxane in the water and oil repellent composition of this embodiment is preferably 500 to 15,000 parts by mass, more preferably 900 to 6,000 parts by mass, per 100 parts by mass of amino-modified silicone.

[0156] From the viewpoints of water repellency, feel, and seam slippage, in the water- and oil-repellent composition of the present embodiment, the mass ratio of silicone resin to alkyl polysiloxane, i.e., silicone resin: alkyl polysiloxane, is preferably 10:90 to 80:20 or 20:80 to 60:40 or 20:80 to 40:60.

[0157] <Polyfunctional isocyanate>

[0158] In one embodiment, the water- and oil-repellent composition may further include a polyfunctional isocyanate as a cross-linking component. As a polyfunctional isocyanate, there is no particular limitation as long as it is a compound having two or more isocyanate groups in the molecule, and known polyisocyanate compounds can be used. As polyfunctional isocyanate, for example, diisocyanate compounds such as alkylene diisocyanate, aryl diisocyanate and cycloalkyl diisocyanate, and modified polyisocyanate compounds such as dimers, trimers or tetramers of these diisocyanate compounds can be mentioned. The number of carbon atoms of alkylene diisocyanate is preferably 1 to 12, the number of carbon atoms of aryl diisocyanate is preferably 6 to 24, and the number of carbon atoms of cycloalkyl diisocyanate is preferably 3 to 24.

[0159] Examples of the diisocyanate compound include 2,4- or 2,6-toluene diisocyanate, ethylene diisocyanate, propylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,4-butane diisocyanate, 1,6-hexamethylene diisocyanate, decanediisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, phenylene diisocyanate, toluene diisocyanate or naphthalene 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-Dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylcyclohexane, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,3-dimethylcyclohexane, 1-methyl-2,4-diisocyanatecyclohexane, 4,4'-methylene-bis(cyclohexyl isocyanate), 3-isocyanate-methyl-3,5,5-trimethylcyclohexyl isocyanate, acid-diisocyanate dimer, ω,ω'-diisocyanate-diethylbenzene, ω,ω'-diisocyanate-dimethyltoluene, ω,ω'-diisocyanate-diethyltoluene, bis(2-isocyanateethyl)fumarate, 1,4-bis(2-isocyanate-prop-2-yl)benzene, and 1,3-bis(2-isocyanate-prop-2-yl)benzene.

[0160] Examples of the triisocyanate compound include triphenylmethane triisocyanate and tris(isocyanatephenyl)-thiophosphate. Examples of the tetraisocyanate compound include dimethyltriphenylmethane tetraisocyanate.

[0161] The modified polyisocyanate compound derived from a diisocyanate compound is not particularly limited as long as it has two or more isocyanate groups. Examples thereof include polyisocyanates having a biuret structure, an isocyanurate structure, a urethane structure, a uretdione structure, an allophanate structure, a trimer structure, and adducts of aliphatic isocyanates of trimethylolpropane. Furthermore, 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.

[0162] The isocyanate group of the polyfunctional isocyanate may be a direct isocyanate group or a blocked isocyanate group blocked by a blocking agent. 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, isopentylphenol, octylphenol, and nonylphenol; lactams such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam; active methylene compounds such as dimethyl malonate, diethyl malonate, acetylacetone, methyl acetoacetate, and ethyl acetoacetate; oximes such as formaldehyde oxime, acetaldehyde oxime, 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 perspective of durable water repellency.

[0163] As the polyfunctional isocyanate, a water-dispersible isocyanate can be used, which is obtained by introducing a hydrophilic group into the polyisocyanate structure to impart a surface active effect, thereby imparting water dispersibility to the polyisocyanate. In addition, in order to promote the reaction between the amino group and the isocyanate group, a known catalyst such as an organotin or organozinc can be used in combination.

[0164] From the viewpoints of water repellency, durable water repellency, and hand feel, the amount of the polyfunctional isocyanate in the water and oil repellent composition of this embodiment is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass, per 100 parts by mass of the amino-modified silicone.

[0165] <Additional water-repellent ingredients>

[0166] The water and oil repellent composition of this embodiment may further contain, as an additional water repellent component, one or more of, for example, known fluorine-based polymers; hydrocarbon group-containing compounds such as aliphatic hydrocarbons, aliphatic carboxylic acids and esters thereof, polyolefins, and poly(meth)acrylates.

[0167] Examples of conventional fluorine-based polymers include NK Gad S-33 (manufactured by Nikka Chemical Co., Ltd.).

[0168] Examples of the aliphatic hydrocarbons include paraffinic hydrocarbons and olefinic hydrocarbons. The aliphatic hydrocarbons preferably have 12 or more carbon atoms.

[0169] The aliphatic carboxylic acid may be either saturated or unsaturated, and preferably has at least 12 carbon atoms. Esterified products of such aliphatic carboxylic acids can be used.

[0170] Examples of the polyolefin include polyethylene, polypropylene, and ethylene-propylene copolymers.

[0171] The carbon number of the hydrocarbon group of the poly (meth) acrylate preferably present via an ester bond is 12 or more. In addition, the carbon number of the hydrocarbon group is preferably 24 or less. The hydrocarbon group may be linear or branched, may be a saturated hydrocarbon or an unsaturated hydrocarbon, and may further have an alicyclic or aromatic ring. Among them, linear is preferred, and linear alkyl is more preferred. The constituent ratio of the monomer of acrylate or methacrylate in such a polymer is preferably 80 to 100% by mass relative to the total amount of the monomer units constituting the polymer. In addition, the weight average molecular weight of such a polymer is preferably measured using gel permeation chromatography, and is more than 30,000 in terms of the value converted to standard polystyrene. In addition, a copolymer of acrylate and methacrylate can be used.

[0172] Examples of such poly(meth)acrylates (non-fluorine-based polymers) include non-fluorine-based acrylic polymers containing a structural unit derived from a (meth)acrylate monomer (A) (hereinafter also referred to as “component (A)”) represented by the following general formula (A-1).

[0173]

[0174] [In formula (A-1), R 1 represents hydrogen, methyl or halogen, R 2 represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent.]

[0175] The (meth)acrylate monomer (A) represented by the general formula (A-1) used in the present embodiment has a monovalent hydrocarbon group with 12 or more carbon atoms which may have a substituent. The hydrocarbon group may be linear or branched, saturated or unsaturated, and may further have an alicyclic or aromatic ring. Among them, a linear one is preferred, and a linear alkyl group is more preferred. In this case, the water repellency is more excellent. When the monovalent hydrocarbon group with 12 or more carbon atoms has a substituent, the substituent may include one or more of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and a (meth)acryloyloxy group. In the present embodiment, in the general formula (A-1), R 2 An unsubstituted hydrocarbon group is preferred.

[0176] The carbon number of the above-mentioned hydrocarbon group is preferably 12 to 40. If the carbon number is more than 12, then when the water- and oil-repellent composition comprising a non-fluorine acrylic polymer is attached to a fiber product, etc., water repellency is easier to improve. On the other hand, if the carbon number is less than 40, then when the water- and oil-repellent composition comprising a non-fluorine acrylic polymer is attached to a fiber product, etc., there is a tendency that the feel of the fiber product further improves.

[0177] 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, water repellency and hand feel are particularly excellent. As the hydrocarbon group, a linear alkyl group having 12 to 22 carbon atoms is particularly preferred.

[0178] 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, and octyl (meth)acrylate. alkyl (meth)acrylate, hexadecyl (meth)acrylate, and triacontyl (meth)acrylate.

[0179] The above-mentioned component (A) may have at least one functional group selected from hydroxyl, amino, carboxyl, epoxy and isocyanate groups that can react with a crosslinking agent. In this case, the durable water repellency of the resulting fiber product can be further improved. The isocyanate group can form a blocked isocyanate group protected by a blocking agent. In addition, when the above-mentioned component (A) has an amino group, the feel of the resulting fiber product can be further improved.

[0180] The component (A) is preferably a monofunctional (meth)acrylate monomer having one polymerizable unsaturated group in one molecule.

[0181] The above-mentioned (A) component may be used alone or in combination of two or more.

[0182] In terms of durable water repellency of the obtained textile product, the component (A) may contain an acrylic acid ester monomer (a1) and a methacrylic acid ester monomer (a2) in combination.

[0183] In terms of water repellency and durable water repellency of the obtained fiber product, the total constituent ratio of the monomers of the above-mentioned component (A) in the non-fluorine-containing acrylic polymer is preferably 50 to 100% by mass, more preferably 55 to 100% by mass, and even more preferably 60 to 100% by mass relative to the total amount of the monomer components constituting the non-fluorine-containing polymer.

[0184] In order to further improve the water repellency of the obtained fiber product and the emulsion stability of the non-fluorinated acrylic polymer during emulsion polymerization or dispersion polymerization and in the composition after polymerization, the non-fluorinated acrylic polymer preferably contains, in addition to the 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 the following general formula (I-1) having an HLB of 7 to 18, (B2) a compound represented by the following general formula (II-1) having an HLB of 7 to 18, and (B3) a compound having an HLB of 7 to 18 in which an alkylene oxide having 2 to 4 carbon atoms is added to an oil or fat having a hydroxyl group and a polymerizable unsaturated group.

[0185]

[0186] [In formula (I-1), R 3 represents hydrogen or methyl, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y 1 It represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.]

[0187]

[0188] [In formula (II-1), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group, Y 2 It represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.]

[0189] The so-called "reactive emulsifier" is an emulsifying dispersant having radical reactivity, that is, a surfactant having one or more polymerizable unsaturated groups in the molecule, and can be copolymerized with a monomer such as (meth)acrylate.

[0190] The HLB of the compounds (B1) to (B3) used in this embodiment is 7 to 18, and in terms of emulsion stability (hereinafter referred to as emulsion stability) in the composition during emulsion polymerization or dispersion polymerization of the non-fluorinated acrylic polymer and after polymerization, it is preferably 9 to 15. Furthermore, in terms of storage stability of the water- and oil-repellent composition, it is more preferred to use two or more reactive emulsifiers (B) having different HLBs within the above range.

[0191] In the reactive emulsifier (B1) represented by the general formula (I-1) used in this embodiment, R 3 is hydrogen or methyl, and is more preferably methyl 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 the emulsification stability of the non-fluorinated acrylic polymer of this embodiment. 1It is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. 1 The type, combination and addition number of the alkyleneoxy groups in the above-mentioned group can be appropriately selected so as to fall within the above-mentioned HLB range. In addition, when there are two or more alkyleneoxy groups, they may have a block addition structure or a random addition structure.

[0192] As the compound represented by the above-mentioned general formula (I-1), a compound represented by the following general formula (I-2) is preferable.

[0193]

[0194] [In formula (I-2), R 3 represents hydrogen or methyl, 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 be within the above-mentioned HLB range. Specifically, it is preferably an integer of 1 to 80. When m is 2 or more, m A 1 O may be the same or different.]

[0195] In the compound represented by the above general formula (I-2), R 3 A is hydrogen or methyl, and is more preferably methyl 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 emulsification stability of the non-fluorinated acrylic polymer. 1 O is an alkyleneoxy group having 2 to 4 carbon atoms. 1 The type and combination of O and the number of m can be appropriately selected so as to be within the above-mentioned HLB range. In terms of the emulsification stability of the non-fluorinated 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 can 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.

[0196] The reactive emulsifier (B1) represented by the general formula (I-2) can be obtained by conventionally known methods and is not particularly limited. In addition, it can be easily obtained from commercially available products, for example, "Ratimeu PD-420", "Ratimeu PD-430", "Ratimeu PD-450" manufactured by Kao Corporation, etc.

[0197] In the reactive emulsifier (B2) represented by the general formula (II-1) used in this embodiment, R 4It is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group, and examples thereof include tridecenyl, tridecadienyl, tetradecenyl, tetradecadienyl, pentadecenyl, pentadecadienyl, pentadecatrienyl, heptadecenyl, heptadecadienyl, heptadecatrienyl, etc. In terms of the emulsion stability of the non-fluorine-based polymer, R 4 More preferably, it is a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

[0198] Y 2 It is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. 2 The type, combination, and number of alkyleneoxy groups in the group can be appropriately selected so as to fall within the aforementioned HLB range. Furthermore, when there are two or more alkyleneoxy groups, they may have a block addition structure or a random addition structure. In terms of the emulsion stability of the non-fluorinated acrylic polymer, the alkyleneoxy group is more preferably an ethyleneoxy group.

[0199] As the compound represented by the above-mentioned general formula (II-1), a compound represented by the following general formula (II-2) is preferable.

[0200]

[0201] [In formula (II-2), R 4 A represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group, 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n can be appropriately selected so as to be within the above-mentioned HLB range. Specifically, it is preferably an integer of 1 to 50. When n is 2 or more, n A 2 O may be the same or different.]

[0202] In the compound represented by the above general formula (II-2), R 4 Examples include the following: 4 Same group.

[0203] A 2 O is an alkyleneoxy group having 2 to 4 carbon atoms. 2 The type and combination of O and the number of n can be appropriately selected so as to fall within the above-mentioned HLB range. 2 O is more preferably an ethyleneoxy group, and n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and further preferably an integer of 8 to 14. When n is 2 or more, n A 2 O can be the same or different. 2When there are two or more types of O, they may have a block addition structure or a random addition structure.

[0204] 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 by a conventionally known method, and is not particularly limited. For example, it can be synthesized by adding a predetermined amount of alkylene oxide at 120 to 170° C. under pressure using an alkaline catalyst such as caustic soda or caustic potash.

[0205] The above-mentioned phenols having corresponding unsaturated hydrocarbon groups include not only pure products or mixtures produced industrially, but also 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, and 3-[11(Z)-pentadecenyl]phenol, which are extracted from cashew nut shells, etc. and are collectively referred to as cardanol.

[0206] The reactive emulsifier (B3) used in this embodiment is a compound having an HLB of 7 to 18, wherein an alkylene oxide having 2 to 4 carbon atoms is added to an oil having a hydroxyl group and a polymerizable unsaturated group. Examples of oils and fats having a hydroxyl 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, ricinoleic acid, 2-hydroxytetracosenoic acid, etc.). In terms of the emulsification stability of the non-fluorine-based polymer, an alkylene oxide adduct of a triglyceride of a fatty acid containing at least one hydroxyunsaturated fatty acid is preferred, an alkylene oxide adduct of castor oil (a triglyceride of a fatty acid containing ricinoleic acid) having 2 to 4 carbon atoms is more preferred, and an ethylene oxide adduct of castor oil is further preferred. Furthermore, the number of moles of the alkylene oxide added can be appropriately selected so as to fall within the aforementioned HLB range. In terms of the emulsion stability of the non-fluorinated acrylic polymer, it is more preferably 20 to 50 moles, and even more preferably 25 to 45 moles. Furthermore, when there are two or more alkylene oxides, they may have a block addition structure or a random addition structure.

[0207] The reactive emulsifier (B3) used in this embodiment can be synthesized by adding an alkylene oxide to an oil or fat having a hydroxyl group and a polymerizable unsaturated group using a conventionally known method, and is not particularly limited. For example, a triglyceride of a fatty acid including ricinoleic acid can be synthesized by adding a predetermined amount of alkylene oxide to castor oil at 120 to 170° C. under pressure using an alkaline catalyst such as caustic soda or caustic potash.

[0208] From the viewpoint of further improving the water repellency of the obtained fiber product and the emulsion stability of the non-fluorinated acrylic polymer, the constituent ratio of the monomer of the component (B) in the non-fluorinated acrylic polymer is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 3 to 10% by mass, based on the total amount of the monomer components constituting the non-fluorinated acrylic polymer.

[0209] In order to further improve the durable water repellency of the obtained fiber product, the non-fluorinated acrylic polymer preferably contains, in addition to the component (A), at least one second (meth)acrylate monomer (C) selected from the following (C1), (C2), (C3), (C4) and (C5) (hereinafter also referred to as "component (C)") as a monomer component.

[0210] (C1) is a (meth)acrylate monomer represented by the following general formula (C-1) except (C5).

[0211]

[0212] [In formula (C-1), R 5 represents hydrogen or methyl, R 6 It represents a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group. The number of (meth)acryloyloxy groups in the molecule is 2 or less.

[0213] (C2) is a (meth)acrylate monomer represented by the following general formula (C-2).

[0214]

[0215] [In formula (C-2), R 7 represents hydrogen or methyl, R 8 represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent.]

[0216] (C3) is a methacrylate monomer represented by the following general formula (C-3).

[0217]

[0218] [In formula (C-3), R 9 represents an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms.]

[0219] (C4) is a (meth)acrylate monomer represented by the following general formula (C-4).

[0220]

[0221] [In formula (C-4), R 10 represents hydrogen or a methyl group, p represents an integer greater than 2, S represents a (p+1)-valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group.]

[0222] (C5) is a (meth)acrylate monomer represented by the following general formula (C-5).

[0223]

[0224] [In formula (C-5), R 11 represents hydrogen or methyl, R 12 It represents a monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms and having at least one functional group selected from a chloro group and a bromo group and a hydroxyl group.

[0225] The monomer (C1) is a (meth)acrylate monomer having a monovalent chain hydrocarbon group with 1 to 11 carbon atoms and at least one functional group selected from a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group in the ester portion, and is a (meth)acrylate monomer other than the above-mentioned (C5). In terms of being able to react with a crosslinking agent, the monovalent chain hydrocarbon group with 1 to 11 carbon atoms preferably has at least one functional group selected from a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. When a non-fluorinated acrylic polymer containing a monomer (C1) having a group capable of reacting with a crosslinking agent is treated with a crosslinking agent together with a fiber product, the durable water repellency can be further improved while maintaining the feel of the resulting fiber product. The isocyanate group can be a blocked isocyanate group protected by a blocking agent.

[0226] The chain hydrocarbon group may be straight-chain or branched, and may be a saturated or unsaturated hydrocarbon group. Furthermore, the chain hydrocarbon group may further have a substituent in addition to the above-mentioned functional group. In particular, straight-chain and / or saturated hydrocarbon groups are preferred in order to further improve the durable water repellency of the resulting fiber product.

[0227] As specific monomers of (C1), 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, etc. can be mentioned. These monomers can 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 fiber products. Furthermore, dimethylaminoethyl (meth)acrylate is preferred in terms of further improving the feel of the resulting fiber products.

[0228] From the viewpoint of water repellency and hand feel of the obtained textile product, the constituent ratio of the monomer (C1) in the non-fluorine-containing acrylic polymer is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass, based on the total amount of monomer components constituting the non-fluorine-containing acrylic polymer.

[0229] The monomer (C2) is a (meth)acrylate monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester portion. Examples of the cyclic hydrocarbon group include isobornyl, cyclohexyl, and dicyclopentyl. These cyclic hydrocarbon groups may have substituents such as alkyl groups. However, when the substituent is a hydrocarbon group, a hydrocarbon group having a total carbon number of 11 or less of the substituent and the cyclic hydrocarbon group is selected. In addition, it is preferred that these cyclic hydrocarbon groups are directly combined with the ester bond from the perspective of further improving durable water repellency. The cyclic hydrocarbon group may be alicyclic or aromatic. In the case of alicyclic, it may be a saturated or unsaturated hydrocarbon group. Specific monomers include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentyl (meth)acrylate. One of these monomers may be used alone, or two or more may be used in combination. Among them, isobornyl (meth)acrylate and cyclohexyl methacrylate are preferred, and isobornyl methacrylate is more preferred, in terms of further improving the durable water repellency of the obtained fiber product.

[0230] From the viewpoint of water repellency and hand feel of the obtained textile product, the constituent ratio of the monomer (C2) in the non-fluorine-containing acrylic polymer is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass, based on the total amount of monomer components constituting the non-fluorine-containing acrylic polymer.

[0231] The monomer (C3) is a methacrylate 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 portion. As the chain hydrocarbon group having 1 to 4 carbon atoms, preferably a straight-chain hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms. As the chain hydrocarbon group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, etc. can be mentioned. As specific compounds, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate can be mentioned. These monomers can be used alone or in combination of two or more. Among them, in terms of further improving the durable water repellency of the obtained fiber product, methyl methacrylate, isopropyl methacrylate, and tert-butyl methacrylate are preferred, and methyl methacrylate is more preferred.

[0232] From the viewpoint of water repellency and hand feel of the obtained fiber product, the constituent ratio of the monomer (C3) in the non-fluorine-containing acrylic polymer is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass, relative to the total amount of monomer components constituting the non-fluorine-containing polymer.

[0233] The monomer of the above-mentioned (C4) is a (meth)acrylate monomer having 3 or more polymerizable unsaturated groups in one molecule. In the present embodiment, it is preferred that T in the above-mentioned general formula (C-4) is a multifunctional (meth)acrylate monomer having 3 or more (meth)acryloyloxy groups in one molecule. In formula (C-4), p Ts may be the same or different. As specific compounds, for example, ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. can be cited. One of these monomers can be used alone, or two or more can be used in combination. Among them, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferred in terms of further improving the durable water repellency of the obtained fiber products.

[0234] From the viewpoint of water repellency and hand feel of the obtained fiber product, the constituent ratio of the monomer (C4) in the non-fluorine-containing acrylic polymer is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass, based on the total amount of monomer components constituting the non-fluorine-containing acrylic polymer.

[0235] The monomer (C5) has at least one functional group selected from chloro and bromo groups and a hydroxyl group and a monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms. 11 In terms of the durable water repellency of the obtained fiber product, R 11 Preferred is methyl.

[0236] R 12 A monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms and having at least one functional group selected from a chloro group and a bromo group and a hydroxyl group. The chain saturated hydrocarbon group may be linear or branched. A linear chain saturated hydrocarbon group exhibits even better durable water repellency in the resulting fiber product. To enhance the durable water repellency of the resulting fiber product, the chain saturated hydrocarbon group preferably has 3 to 4 carbon atoms, more preferably 3 carbon atoms.

[0237] In terms of the durable water repellency of the obtained fiber product, the chain saturated hydrocarbon group preferably has one or two chloro groups and one hydroxyl group, and more preferably has one chloro group and one hydroxyl group. In addition, in terms of the durable water repellency of the obtained fiber product, the chain saturated hydrocarbon group is further preferably at the β position (with CH2=CR 11 The carbon atom adjacent to the carbon atom to which the (CO)O-bond is attached) has a hydroxyl group. Specific examples of the chain saturated hydrocarbon group include 3-chloro-2-hydroxypropyl, 3-chloro-2-hydroxybutyl, 5-chloro-2-hydroxypentyl, 3-chloro-2-hydroxy-2-methylpropyl, and 3-bromo-2-hydroxypropyl.

[0238] 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, as it can further improve the durable water repellency of the resulting fiber product.

[0239] In terms of durable water repellency of the obtained fiber product, the constituent ratio of the monomer (C5) in the non-fluorine-containing acrylic polymer is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass, based on the total amount of monomer components constituting the non-fluorine-containing acrylic polymer.

[0240] From the viewpoint of water repellency and hand feel of the obtained textile product, the total constituent ratio of the monomers of the component (C) in the non-fluorine-containing acrylic polymer is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass, based on the total amount of monomer components constituting the non-fluorine-containing acrylic polymer.

[0241] The fluorine-free acrylic polymer may contain, in addition to the components (A), (B) and (C), a monofunctional monomer (D) copolymerizable with these components (hereinafter also referred to as "component (D)") within a range not impairing the effects of the present invention.

[0242] Examples of the monomer (D) include (meth)acryloylmorpholine, (meth)acrylates having a hydrocarbon group other than components (A) and (C), (meth)acrylic acid, fumarates, maleates, fumaric acid, maleic acid, (meth)acrylamide, N-methylol acrylamide, vinyl ethers, vinyl esters, ethylene, styrene, and other vinyl monomers other than component (E) described below that do not contain fluorine. It should be noted that the (meth)acrylates having a hydrocarbon group other than components (A) and (C) may have a substituent such as a vinyl group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, or a blocked isocyanate group on the hydrocarbon group; may have a substituent other than a group reactive with a crosslinking agent such as a quaternary ammonium group; and may have an ether bond, an ester bond, an amide bond, or a urethane bond. Examples of the (meth)acrylate other than the component (A) and the component (C) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and ethylene glycol di(meth)acrylate.

[0243] From the viewpoint of water repellency and hand feel of the obtained textile product, the constituent ratio of the monomer of the component (D) in the non-fluorinated acrylic polymer is preferably 10% by mass or less based on the total amount of monomer components constituting the non-fluorinated acrylic polymer.

[0244] To further enhance the durable water repellency of the resulting fiber product, the non-fluorinated acrylic polymer preferably has at least one functional group selected from the group consisting of hydroxyl, amino, carboxyl, epoxy, and isocyanate groups that is reactive with a crosslinking agent. The isocyanate group may be a blocked isocyanate group protected by a blocking agent. Furthermore, to further enhance the feel of the resulting fiber product, the non-fluorinated acrylic polymer preferably has an amino group.

[0245] In order to further improve the water repellency and peel strength against coatings of the resulting fiber product, the non-fluorinated acrylic polymer preferably contains, in addition to the component (A), at least one monomer (E) selected from vinyl chloride and vinylidene chloride (hereinafter also referred to as "component (E)") as a monomer component.

[0246] In view of the water repellency and peel strength against the coating material of the obtained fiber product, at least one monomer (E) selected from vinyl chloride and vinylidene chloride used in the present embodiment is preferably vinyl chloride.

[0247] From the viewpoint of further improving the peel strength of the obtained fiber product against the coating, the constituent ratio of the monomer of the component (E) in the non-fluorine-containing acrylic polymer is preferably 1 to 45% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 35% by mass, based on the total amount of the monomer components constituting the non-fluorine-containing acrylic polymer.

[0248] The method for producing the non-fluorine acrylic polymer will be described.

[0249] The non-fluorine acrylic polymer can be produced by free radical polymerization. In this free radical polymerization, emulsion polymerization or dispersion polymerization is preferably used from the viewpoint of the performance of the resulting water- and oil-repellent and the environment.

[0250] For example, a non-fluorine acrylic polymer can be obtained by emulsion polymerization or dispersion polymerization of the (meth)acrylate monomer (A) represented by the general formula (A-1) in a medium. More specifically, for example, by adding component (A) and, as needed, component (B), component (C), component (D), and component (E), as well as an emulsifying aid or a dispersing aid, to a medium, the mixed solution is emulsified or dispersed to obtain an emulsion or a dispersion. By adding a polymerization initiator to the obtained emulsion or dispersion, a polymerization reaction can be initiated to polymerize the monomer and the reactive emulsifier. It should be noted that as means for emulsifying or dispersing the above-mentioned mixed solution, a homogenizer, a high-pressure emulsifier, or ultrasonic waves can be cited.

[0251] As the above-mentioned emulsifying aid or dispersing aid etc. (hereinafter, also referred to as "emulsifying aid etc."), one or more selected from nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants other than the above-mentioned reactive emulsifier (B) can be used. The content of the emulsifying aid etc. is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and further preferably 1 to 10 parts by mass relative to 100 parts by mass of all monomers. If the content of the above-mentioned emulsifying aid etc. is 0.5 parts by mass or more, there is a tendency that the dispersion stability of the mixed solution is further improved, and if the content of the emulsifying aid etc. is 30 parts by mass or less, there is a tendency that the water repellency of the obtained water- and oil-repellent composition is further improved.

[0252] As the medium for emulsion polymerization or dispersion polymerization, water is preferably used, and water can 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. It should be noted that the ratio of water to organic solvent is not particularly limited.

[0253] As the polymerization initiator, known polymerization initiators such as azo-based, peroxide-based, or redox-based polymerization initiators can be used as appropriate. The polymerization initiator content is preferably 0.01 to 2 parts by mass relative to 100 parts by mass of the total monomers. When the polymerization initiator content is within this range, a non-fluorinated acrylic polymer having a weight-average molecular weight of 100,000 or greater can be efficiently produced.

[0254] Furthermore, in the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or tert-butyl alcohol may be used for the purpose of adjusting the molecular weight.

[0255] In addition, a polymerization inhibitor may be used to adjust the molecular weight. By adding a polymerization inhibitor, a non-fluorinated acrylic polymer having a desired weight average molecular weight can be easily obtained.

[0256] The polymerization reaction temperature is preferably 20° C. to 150° C. When the temperature is 20° C. or higher, polymerization tends to be sufficient, while when the temperature is 150° C. or lower, control of the reaction heat becomes easy.

[0257] During 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 polymerization initiator, chain transfer agent, and polymerization inhibitor. The melt viscosity at 105°C can be adjusted by increasing or decreasing the contents of the multifunctional monomer and the polymerization initiator. It should be noted that to lower the melt viscosity at 105°C, it is sufficient to reduce the content of the monomer having two or more polymerizable functional groups or to increase the content of the polymerization initiator.

[0258] From the viewpoint of storage stability and handleability of the composition, 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% by mass, more preferably 20 to 40% by mass, based on the total amount of the emulsion or dispersion.

[0259] Examples of the hydrocarbyl group-containing compound include, for example, NR-90 (manufactured by Nikka Chemical Co., Ltd.), NR-158 (manufactured by Nikka Chemical Co., Ltd.), TH-44 (manufactured by Nikka Chemical Co., Ltd.), and PW-182 (Daichi Chemical Co., Ltd.). Wakaba Chemical Co., Ltd.), RSH (manufactured by Hwa Chemical Co., Ltd.), RSH (manufactured by Hwa Chemical Co., Ltd.), and Porcup E CO-500 (manufactured by Ohara Biochemical Co., Ltd.), NX018 (manufactured by Nana Chemical Co., Ltd.), etc.

[0260] <Other ingredients>

[0261] The water- and oil-repellent composition of the present embodiment may further contain, in addition to the components described above, a surfactant, a defoaming agent, an organic acid, an inorganic acid, an alcohol, an antibacterial agent, an antifungal agent, a pH regulator, a colorant, silica, an antioxidant, a deodorant, various catalysts, an emulsion stabilizer, various organic solvents, a chelating agent, an antistatic agent, an organic modified silicone other than amino-modified silicone, a cross-linking agent other than polyfunctional isocyanate, and the like.

[0262] The surfactant must include a polyoxyalkylene adduct and may further include other surfactants. Other surfactants that can be used, for example, are those that have the function of expanding the temperature range in which the emulsion is stably maintained or adjusting the amount of foaming generated when mixed with water to prepare a diluent. The other surfactant may be any one of a nonionic surfactant, an anionic surfactant, a cationic surfactant, or an amphoteric surfactant. Other surfactants may be used alone or in combination of two or more.

[0263] 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; alcohol-based defoaming agents such as polyoxyalkylene monool, di-tert-amylphenoxyethanol, 3-heptyl alcohol, and 2-ethylhexanol; ether-based defoaming agents such as di-tert-amylphenoxyethanol, 3-heptyl cellosolve, nonyl cellosolve, and 3-heptyl carbitol; phosphate-based defoaming agents such as tributyl phosphate and tris(butoxyethyl) phosphate; amine-based defoaming agents such as diamylamine; amide-based defoaming agents such as polyalkylene amides and acylated polyamines; sulfate-based defoaming agents such as sodium lauryl sulfate; and mineral oil. The defoaming agents may be used alone or in combination of two or more.

[0264] 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, and toluenesulfonic acid. The organic acid may be used alone or in combination of two or more.

[0265] The inorganic acid is not particularly limited, and examples thereof include hydrogen chloride, sulfuric acid, nitric acid, etc. The inorganic acid may be used alone or in combination of two or more.

[0266] The alcohol is not particularly limited, and examples thereof include ethanol, isopropyl alcohol, glycerin, trimethylolpropane, diethylene glycol, triethylene glycol, dipropylene glycol, propylene glycol, etc. The alcohol may be used alone or in combination of two or more.

[0267] As antistatic agent, it is good to use the material that is difficult for hindering the performance of water repellency. As antistatic agent, for example, can enumerate, the nonionic surfactants such as cationic surfactants such as higher alcohol sulfate, sulfated oil, sulfonate, quaternary ammonium salt, imidazoline type quaternary salt, polyethylene glycol type, polyol ester type etc., imidazoline type quaternary salt, alanine type, betaine type etc., as high molecular compound type, can enumerate above-mentioned antistatic polymer, polyalkylamine etc. Antistatic agent can be used alone 1 kind or be used in combination of 2 or more.

[0268] Examples of cross-linking agents other than the above-mentioned polyfunctional isocyanate include melamine resins and glyoxal resins.

[0269] Melamine resins that can be used include compounds having a melamine skeleton, such as polymethylolmelamines such as trimethylolmelamine and hexamethylolmelamine; alkoxymethylmelamines in which some or all of the methylol groups of the polymethylolmelamine are replaced with alkoxymethyl groups having an alkyl group having 1 to 6 carbon atoms; and acyloxymethylmelamines in which some or all of the methylol groups of the polymethylolmelamine are replaced with acyloxymethyl groups having acyl groups having 2 to 6 carbon atoms. These melamine resins may be monomers or multimers of dimers or higher, or mixtures thereof may be used. Furthermore, melamine resins obtained by co-condensing urea or the like with a portion of the melamine may also be used. Examples of such melamine resins include ベッカミンAPM, ベッカミンM-3, ベッカミンM-3(60), ベッカミンMA-S, and ベッッカミンMA-S manufactured by DIC Co., Ltd. Kumin J-101 and Kumin J-101LF, Kumikum 380K manufactured by Kumikro Chemical Industry Co., Ltd., Kumiko MM series manufactured by Miki Riken Industry Co., Ltd., etc.

[0270] As the glyoxal resin, any known substance can be used. Examples of the glyoxal resin include 1,3-dimethylglyoxal urea resin, dimethylol dihydroxy ethylene urea resin, and dimethylol dihydroxy propylene urea resin. The functional groups of these resins may be substituted with other functional groups. Examples of such glyoxal resins include Pulse Micron N-80 and Pycno Mining NS-manufactured by DIC Co., Ltd. 11. ベッカミンLF-K, ベッカミンNS-19, ベッカミンLF-55Pコンク, ベッカミンN S-210L, Pulmonium NS-200, Pulmonium NF-3, Pulmonium Chemical Industry Co., Ltd.レジンGS-20E, リケンレジンRG series and リケンレジンMS series manufactured by Miki Riken Industrial Co., Ltd.

[0271] From the viewpoint of promoting the reaction, it is preferred to use a catalyst in melamine resin and glyoxal resin. As such a catalyst, as long as it is a catalyst commonly used, there is no particular limitation, and for example, borofluorinated compounds such as ammonium borofluoride and zinc borofluoride can be cited; neutral metal salt catalysts such as magnesium chloride and magnesium sulfate; inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, etc. Among these catalysts, as required, as a co-catalyst, organic acids such as citric acid, tartaric acid, malic acid, maleic acid, lactic acid, etc. can also be used. Examples of such catalysts include Kornet ACX, Kornet 376, and Kornet manufactured by DIC Co., Ltd. O, Kirin M, Kirin G (GT), Kirin X-110, Kirin GT-3 and Kirin GT-3 NFC-1, ユニカキャタリスト3-P manufactured by ユニオン Chemical Industry Co., Ltd. and ユニカキャタリストMC-109, three The Ricoh RC series, the Ricoh MX series and the Ricoh RZ-5 made by Kiuriken Industry Co., Ltd.

[0272] The water- and oil-repellent composition according to the present embodiment can be suitably used in applications such as a fiber product processing agent, a paper product processing agent, and a leather product processing agent.

[0273] 《Method for producing water- and oil-repellent composition》

[0274] The present embodiment also provides the manufacture method of the water- and oil-repellent composition of the present embodiment.The water- and oil-repellent composition of the present embodiment can be manufactured by carrying out emulsification dispersion about the above-mentioned constituent of said composition.For example, can be by making silicone resin be dissolved in organic solvent, use emulsifier and aqueous medium to carry out emulsification dispersion thereby obtain (emulsified dispersion of silicone resin).

[0275] When the water- and oil-repellent composition contains at least one selected from amino-modified silicone, alkyl polysiloxane and polyfunctional isocyanate, it can be obtained by dissolving the silicone resin and at least one selected from amino-modified silicone, alkyl polysiloxane and polyfunctional isocyanate in an organic solvent and emulsifying and dispersing using an emulsifier and an aqueous medium.

[0276] In the case where water- and oil-repellent composition comprises at least one selected from amino-modified silicone, alkyl polysiloxane and polyfunctional isocyanate, 1 formulation for mixing in advance at least one selected from silicone resin and amino-modified silicone, alkyl polysiloxane and polyfunctional isocyanate can be, for example, by making the emulsified dispersion of silicone resin and at least one selected from amino-modified silicone, alkyl polysiloxane and polyfunctional isocyanate be dissolved in organic solvent, 2 formulations of the emulsified dispersion obtained using emulsifying agent and aqueous medium, can be 3 formulations, 4 formulations etc. They can also be mixed and made into water- and oil-repellent composition, it is also possible to further carry out high-pressure homogenizer processing etc. and make water- and oil-repellent composition.

[0277] From the viewpoint of ease of handling, the water / oil repellent composition of the present embodiment is preferably in a one-part or two-part form.

[0278] As the method for dispersing the above-mentioned each component in the aqueous medium, for example, each component, the organic solvent of the present embodiment, the aqueous medium of the present embodiment and the emulsifier of the present embodiment are mixed and stirred. When mixed and stirred, known emulsifying and dispersing machines such as a micro-dryer, a high-speed stirrer, a homogenizer, an ultrasonic homogenizer, a homomixer, a bead mill, a bead mill, a Dai Nuo mill, an Aspek Mill, a basket mill, a ball mill, a Nanomai Za, an Alchi Mai Za, and a Star Bastor can be used. These emulsifying and dispersing machines can be used alone or in combination of two or more.

[0279] As the aqueous medium, various organic solvents exemplified in the above-mentioned section <Aqueous Medium> can be used. The aqueous medium can be contained in the water- and oil-repellent composition as a mixed solvent with water.

[0280] From the viewpoint of dispersion stability, the dispersion may further include a surfactant. Such a surfactant is not particularly limited as long as it can improve the emulsified dispersion stability, and examples thereof include well-known nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. These may be used alone or in combination of two or more.

[0281] As the water- and oil-repellent composition of the above-mentioned dispersion liquid, it can be used directly as a treatment liquid, or it can be made into a treatment liquid by further diluting with an aqueous medium or a hydrophobic organic solvent. In one embodiment, the water- and oil-repellent composition or the treatment liquid can include, for example, 0.5 to 70 mass % or 1 to 50 mass % or 1.5 to 45 mass % of a silicone resin, an amino-modified silicone, and an alkyl polysiloxane. The treatment liquid includes, for example, polyfunctional isocyanates and other cross-linking agents in an amount of 0.1 to 5.0 mass % or 0.2 to 3.0 mass % or 0.3 to 2.0 mass %.

[0282] Water- and oil-repellent fiber products and methods for producing the same

[0283] The present embodiment further provides a water- and oil-repellent fiber product and a manufacturing method. In one embodiment, the water- and oil-repellent fiber product of the present embodiment can be manufactured by a method having a process of treating a fiber with a treatment solution comprising the water- and oil-repellent composition of the present embodiment. In one embodiment, the water- and oil-repellent fiber product is formed by treating the fiber product with the water- and oil-repellent composition of the present embodiment (i.e., water- and oil-repellent treatment). In one embodiment, the water- and oil-repellent fiber product comprises the above-mentioned silicone resin as a component of the water- and oil-repellent composition, an organic solvent whose amount of water required to dissolve 1g of organic solvent exceeds 10mL at 20°C, an emulsifier, and an aqueous medium, and optionally further comprises the above-mentioned organic solvent and / or aqueous medium.

[0284] The raw materials of the fibers are 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 fibers may be in the form of yarn, cloth, nonwoven fabric, paper, or the like. The fibers may also be fiber products.

[0285] As a method for treating fiber with a treatment solution comprising the water- and oil-repellent composition of the present embodiment, for example, when the water- and oil-repellent composition comprises a silicone resin and at least one selected from amino-modified silicone, alkyl polysiloxane and polyfunctional isocyanate, it can be enumerated as follows: a method for treating by 1 process using a treatment solution comprising a silicone resin and at least one selected from amino-modified silicone, alkyl polysiloxane and polyfunctional isocyanate; a method for treating by 2 processes, 3 processes, 4 processes, etc. using a treatment solution comprising at least 1 component of the above-mentioned 4 components and a treatment solution comprising at least 1 other component. When treated by 2 processes to 4 processes, the order in which each component is treated can be any order.

[0286] Examples of methods for treating the fibers with the treatment liquid include immersion, spraying, and coating. When the water- and oil-repellent composition contains water, it is preferably dried to remove the water after adhering to the fibers.

[0287] The water- and oil-repellent composition of the present embodiment can suitably adjust the attachment amount of fiber according to the degree of required water repellency, preferably with respect to fiber 100g, the attachment amount of water- and oil-repellent composition (the total attachment amount of silicone resin, amino-modified silicone and alkyl polysiloxane in one scheme) becomes the mode adjustment of 0.1~5g, more preferably with the mode adjustment of becoming 0.1~3g.If the attachment amount of water- and oil-repellent composition is less than 0.1g, then there is the tendency that fiber can not bring into play sufficient water repellency, if more than 5g, then there is the tendency that becomes disadvantageous economically.This attachment amount is for example confirmed by the method for carrying out solvent extraction from water-repellent fiber product.

[0288] Furthermore, after the water- and oil-repellent composition of this embodiment is attached to the fibers, it is preferably subjected to a heat treatment. The temperature conditions are not particularly limited, but from the perspectives of water repellency, durable water repellency, and hand feel, it is preferably performed at 110 to 180°C for 1 to 5 minutes.

[0289] In view of its excellent water repellency and soft feel, the water- and oil-repellent fiber product of this embodiment is suitable for use in fiber applications such as down side cloths, coats, jackets, windbreakers, women's shirts, formal shirts, skirts, women's trousers, gloves, hats, bedding side cloths, bedding drying covers, curtains or tents, and other clothing products, as well as non-clothing products.

[0290] Example

[0291] The present invention is further described below by way of examples, but the present invention is not limited by these examples.

[0292] <Manufacturing of Silicone Dispersion>

[0293] [Materials used]

[0294] (Silicone resin)

[0295] MQ-1600: Made by Dow Chemical

[0296] (Organic solvent)

[0297] Isoparaffin: IP-2028, manufactured by Idemitsu Kosan Co., Ltd., an isoparaffin with 10 to 16 carbon atoms. The amount of water required to dissolve 1g of organic solvent: more than 1000mL

[0298] Mineral oil: Ecosol D-40 manufactured by Idemitsu Kosan Co., Ltd., kinematic viscosity at 30°C: 20 mm2 / s, the amount of water required to dissolve 1g of organic solvent: more than 1000mL

[0299] Mineral spirits: manufactured by Toyo Petrochemical Co., Ltd., boiling point: 180-200°C, amount of water required to dissolve 1g of organic solvent: more than 1000mL

[0300] (Aqueous medium)

[0301] Isopropyl alcohol: manufactured by Sankyo Chemical Co., Ltd. The amount of water required to dissolve 1g of organic solvent: 1mL or less Tripropylene glycol: manufactured by ADEKA Co., Ltd. The amount of water required to dissolve 1g of organic solvent: 1mL or less

[0302] (Alkyl polysiloxane)

[0303] Dimethyl silicone 1: DOWSIL TM SH 200C Fluid 5 cSt (manufactured by DowToray), JIS K 2283: 2000 (Ubbelohde viscometer), viscosity measured at (25°C): 5 cps

[0304] Dimethyl silicone 2: DOWSIL TM SH 200 Fluid 100 cSt (manufactured by DowToray), JIS K2283: 2000 (Ubbelohde viscometer), viscosity measured at (25°C): 100 cps

[0305] Dimethyl silicone 3: DOWSIL TM SH 200 Fluid 100 cSt (manufactured by DowToray), JIS K2283: 2000 (Ubbelohde viscometer), viscosity measured at (25°C): 1000 cps

[0306] Dimethyl silicone 4: DOWSIL TM SH 200 Fluid 100 cSt (manufactured by DowToray), JIS K2283: 2000 (Ubbelohde viscometer), viscosity measured at (25°C): 10,000 cps

[0307] (Amino-modified silicone)

[0308] Monoamine at both ends: BY16-853U (manufactured by Dow Toray), functional group equivalent weight: 460

[0309] Side chain diamine 1: KF-8005 (manufactured by Shin-Etsu Chemical Co., Ltd.), functional group equivalent weight: 11000

[0310] Side chain diamine 2: SF-8417 (manufactured by DowToray), functional group equivalent weight: 1800

[0311] Side chain diamine 3: KF-393 (manufactured by Shin-Etsu Chemical Co., Ltd.), functional group equivalent weight: 350

[0312] Side chain monoamine: KF-864 (manufactured by Shin-Etsu Chemical Co., Ltd.), functional group equivalent weight: 3800

[0313] (Emulsifier: nonionic surfactant)

[0314] Polyoxyethylene (7 mol) isodecyl ether: a synthetic product obtained by adding ethylene oxide (7 mol) to isodecyl alcohol (1 mol) according to a conventional method, HLB: 13.2

[0315] Polyoxyethylene (9 mol) isodecyl ether: a synthetic product obtained by adding ethylene oxide (9 mol) to isodecyl alcohol (1 mol) according to a conventional method, HLB: 14.3

[0316] (Emulsifier: cationic surfactant)

[0317] Rikaru T-28: Stearyltrimethylammonium chloride manufactured by Rakuro Co., Ltd.

[0318] [Production Example 1]

[0319] In a flask, 200g of isoparaffin and 250g of MQ-1600 (as a silicone resin) were added and dissolved while heating at 80°C. 25g of polyoxyethylene (7 moles) isodecyl ether (as a nonionic surfactant), 5.0g of Lipocard T-28 (as a cationic surfactant) and pure water were added thereto, and the mixture was processed with a high-pressure homogenizer (APV GAULIN Inc., Model 15MR-8TBA) at 300 bar to obtain a dispersion comprising 25% by mass of a silicone resin as a water- and oil-repellent component.

[0320] [Production Examples 2 to 19]

[0321] The same procedure as in Production Example 1 was carried out except that the blending was performed as shown in Table 1, thereby obtaining a dispersion containing 25% by mass in total of the silicone resin, amino-modified silicone, and alkyl polysiloxane as water- and oil-repellent components.

[0322] <Manufacturing of cross-linking component dispersion>

[0323] [Cross-linking component dispersion 1]

[0324] (1,6-Hexanediisocyanate (HDI) biuret blocked with dimethylpyrazole (DMP))

[0325] To a reaction vessel, 1 mol of Duranet 24A-100 (biuret-type hexamethylene diisocyanate, NCO functional group number: 3, content 100% by mass, manufactured by Asahi Kasei Chemicals Co., Ltd.) and methyl isobutyl ketone were added, and the mixture was heated to 60-70°C. Subsequently, 3 mol of 3,5-dimethylpyrazole was slowly added, and the mixture was reacted at 60-70°C until the isocyanate content, as confirmed by an infrared spectrophotometer, reached zero. This yielded a colorless, transparent, viscous liquid composition containing 98.7% by mass of a dimethylpyrazole-blocked polyisocyanate compound.

[0326] 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 a 30-mol ethylene oxide adduct of tristyrenated phenol as a nonionic surfactant were mixed and homogenized. Water was slowly added while stirring, and the mixture was homogenized at 30 MPa to obtain a crosslinking component dispersion 1 containing 40% by mass of a dimethylpyrazole-blocked form of hexamethylene diisocyanate biuret.

[0327] [Cross-linking component dispersion 2]

[0328] In a reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen 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) as a solvent were mixed at room temperature (25°C). 59.6 g (0.62 mol) of dimethylpyrazole (hereinafter sometimes abbreviated as DMP, Tokyo Chemical Industry) was added in several portions as a blocking agent so that the temperature of the reaction solution did not exceed 50°C, and the mixture was stirred for 1 hour. Then, a Fourier transform infrared (FT-IR) spectrum was measured, and a peak derived from the NCO group (2260 cm) was confirmed. -1 Next, 21 g of Noigen XL-40 (HLB 10.5, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was added, and pure water was added in small portions while mixing to obtain a crosslinking component dispersion 2 containing 20% by mass of an IPDI trimer / DMP blocked product.

[0329] [Cross-linking component dispersion 3]

[0330] (TDI / TMP / MEKO: A dispersion of a methyl ethyl ketoxime (MEKO)-blocked product of the reaction product of trimethylolpropane (TMP) and toluene diisocyanate (TDI))

[0331] First, Polurene AD (75% by mass of the reaction product of trimethylolpropane and toluene diisocyanate (mass ratio of 2,4-isomer to 2,6-isomer: 80:20), solvent: ethyl acetate, manufactured by SAPICI, trade name) was prepared as a reaction product of trimethylolpropane and toluene diisocyanate.

[0332] One mole of the reaction product of trimethylolpropane and toluene diisocyanate prepared above was heated to 60-70°C. Subsequently, 3 moles of methyl ethyl ketone oxime was slowly added, and the reaction was allowed to proceed at 60-70°C until the isocyanate content, as confirmed by an infrared spectrophotometer, reached zero. Ethyl acetate was then added to obtain a colorless, transparent, viscous liquid composition containing 98.7% by mass of a methyl ethyl ketone oxime-blocked polyisocyanate compound.

[0333] 180 parts by mass of the composition obtained above and 20 parts by mass of a 30-mol ethylene oxide adduct of tristyrenated phenol as a nonionic surfactant were mixed and homogenized. Water was slowly added while stirring, and the mixture was homogenized at 30 MPa to obtain a dispersion containing 40% by mass of a methyl ethyl ketoxime-blocked product of the reaction product of trimethylolpropane and toluene diisocyanate.

[0334] <Production of acrylic dispersion>

[0335] [Materials used]

[0336] (Acrylic monomer a)

[0337] Stearyl acrylate: manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0338] Stearyl methacrylate: manufactured by Tokyo Chemical Industry Co., Ltd.

[0339] Behenyl methacrylate: manufactured by BASF

[0340] (Acrylic monomer c)

[0341] Diacetone acrylamide: manufactured by Tokyo Chemical Industry Co., Ltd.

[0342] (Acrylic monomer b)

[0343] Vinyl chloride: Made by AGC Corporation

[0344] (Nonionic surfactant)

[0345] Noigen XL-40: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 10.5

[0346] Noigen XL-60: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 12.5

[0347] Noigen XL-100: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7

[0348] (Alkyl modified silicone)

[0349] Silwax L118: Made by Siltech, octadecyl dimethicone

[0350] Silwax D222: Made by Siltech, Behenyl Dimethicone

[0351] Silwax J1032: Made by Siltech, C32 alkyl polydimethylsiloxane

[0352] (Cationic surfactant)

[0353] Stearyltrimethylammonium chloride: Made by Rakuten·Surface Co., Ltd.

[0354] (Organic solvent)

[0355] Tripropylene glycol: Made by ADEKA

[0356] (Polymerization initiator)

[0357] Azobis(isobutylamidine) dihydrochloride: manufactured by Fujifilm Wako Junyao Co., Ltd.

[0358] [Production Example 20]

[0359] 15.6 g of stearyl acrylate, 0.4 g of diacetone acrylamide, 0.8 g of Noigen XL-1000, 0.2 g of stearyltrimethylammonium sulfate, 10 g of tripropylene glycol, and 68.8 g of water were placed in an autoclave and stirred at 45° C. to form a mixed solution. Ultrasonic waves were irradiated into the mixed solution to emulsify and disperse all the monomers.

[0360] Next, 0.2 g of azobis(isobutylamidine) dihydrochloride was added to the dispersion, and under a nitrogen atmosphere, 4.0 g of vinyl chloride was continuously pressure-added so as to maintain the internal pressure of the autoclave at 0.3 MPa, while radical polymerization was carried out at 60° C. for 6 hours to obtain a dispersion containing 20% by mass of an acrylic resin.

[0361] [Production Examples 21 and 22]

[0362] According to the addition amounts shown in Table 2, the same procedure as in Production Example 20 was followed to obtain a dispersion containing 20% by mass of an acrylic resin.

[0363] [Production Example 23]

[0364] 13.6 g of stearyl acrylate, 0.4 g of diacetone acrylamide, 2.0 g of Silwax L118, 0.8 g of Noigen XL-100, 0.2 g of stearyltrimethylammonium sulfate, 10 g of tripropylene glycol, and 68.8 g of water were placed in an autoclave and mixed and stirred at 45°C to prepare a mixed liquid. Ultrasonic waves were then irradiated into the mixed liquid to emulsify and disperse all the monomers.

[0365] Next, 0.2 g of azobis(isobutylamidine) dihydrochloride was added to the dispersion, and under a nitrogen atmosphere, 4.0 g of vinyl chloride was continuously pressure-added so as to maintain the internal pressure of the autoclave at 0.3 MPa, while radical polymerization was carried out at 60° C. for 6 hours to obtain a dispersion containing 20% by mass of an acrylic resin.

[0366] [Production Examples 24 and 25]

[0367] According to the addition amount shown in Table 2, a dispersion containing 20% by mass of acrylic resin was obtained by the same method as in Production Example 23.

[0368] <Production of Water- and Oil-Repellent Composition and Water- and Oil-Repellent Fiber Product>

[0369] As the fiber products, dyed polyester (PET) 100% fabric and dyed nylon (Ny) 100% fabric were used.

[0370] [Example 1]

[0371] The organosilicon dispersion obtained in manufacture example 1 and cross-linked component dispersion 1 are diluted with pure water in a manner such that the organosilicon dispersion becomes 5 mass %, the cross-linked component dispersion 1 becomes 0.5 mass % and a water- and oil-repellent composition is produced. Using this water- and oil-repellent composition as a treatment solution, dyed polyester 100% cloth and dyed nylon 100% cloth are each immersed in the treatment solution (liquid removal rate 60 mass %) and then dried at 130°C for 1 minute. The mixture is then heat-treated at 170°C for 1 minute to obtain a water- and oil-repellent fiber product.

[0372] [Examples 2 to 37, Comparative Examples 1 to 3]

[0373] The same procedure as in Example 1 was carried out except that the silicone dispersion, the acrylic dispersion, and the crosslinking component dispersion 1 were as shown in Tables 3 and 4.

[0374] <Evaluation>

[0375] [Amount of water required to dissolve 1g of organic solvent]

[0376] The amount of water required to dissolve 1 g of the organic solvent used in each Production Example was evaluated in accordance with JIS K8001:2017 3.2, "Terms indicating the degree of solubility." This was determined by adding 1 g of the organic solvent to a certain amount of water, vigorously shaking the mixture for 30 seconds every 5 minutes at 20°C ± 5°C, and evaluating the volume (mL) of water required to dissolve 1 g of the organic solvent 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. Dissolution of 1 g of the organic solvent within 30 minutes under these conditions was investigated using the following evaluation criteria.

[0377] (Evaluation criteria for the amount of water required to dissolve 1 g of organic solvent)

[0378] Less than 1 mL: Dissolve in 1 mL of water within 30 minutes.

[0379] More than 1 mL and less than 10 mL: Does not dissolve in 1 mL of water within 30 minutes, but dissolves in 10 mL of water within 30 minutes.

[0380] More than 10 mL and less than 30 mL: Does not dissolve in 10 mL of water within 30 minutes, but dissolves in 30 mL of water within 30 minutes.

[0381] More than 30 mL and less than 100 mL: Does not dissolve in 30 mL of water within 30 minutes, but dissolves in 100 mL of water within 30 minutes.

[0382] More than 100 mL and less than 1000 mL: Does not dissolve in 100 mL of water within 30 minutes, but dissolves in 1000 mL of water within 30 minutes.

[0383] Over 1000mL: Will not dissolve in 1000mL of water within 30 minutes.

[0384] [Product Stability of Water- and Oil-Repellent Composition]

[0385] The product stability of the water- and oil-repellent composition was evaluated by centrifugation. 100 g of the water- and oil-repellent composition was weighed in a 1 L centrifuge bottle, covered, and centrifuged at 20°C, 8000 rpm for 30 minutes. The supernatant after centrifugation was transferred to another container and its mass was weighed. The sedimentation rate was calculated according to the following formula.

[0386] Sedimentation rate (%) = {(mass of the water- and oil-repellent composition weighed in the centrifuge bottle) - (mass of the supernatant)} / 100

[0387] The smaller the sedimentation rate, the better the stability of the product.

[0388] [Processing stability of water- and oil-repellent composition]

[0389] The processing stability of water- and oil-repellent composition was evaluated by homomixer test. Water- and oil-repellent composition was diluted to 5% by mass with pure water, using homomixer (Platinum Co., Ltd. system, model: TK Robomix D162 homomixer MARKII), after being stirred at room temperature (25 ° C) for 10 minutes with 5000rpm, it was allowed to stand for 10 minutes. Black cotton cloth was filtered and the state of black cotton cloth was evaluated in 5 stages (with reference to Figure 1 ).

[0390] 5: No precipitate at all

[0391] 4: Fewer precipitates were observed

[0392] 3: Precipitate is observed along the hole of the Buchner funnel

[0393] 2: Confirm that the precipitate covers the entire surface of the cotton cloth

[0394] 1: Confirmed accumulation of precipitates covering the entire surface of the cotton cloth

[0395] [Water repellency of water- and oil-repellent fiber products]

[0396] Water repellency testing was conducted using the spray method of JIS L1092 (2009) at a spray water temperature of 20°C. The results were visually evaluated using the following grades. Note that slightly good properties were assigned a "+" grade, while properties between grades 4 and 5 were assigned a grade of "4-5."

[0397] The evaluation criteria for water repellency are as follows.

[0398] Water repellency: status

[0399] 5: There is no moisture attached to the surface

[0400] 4: Slightly wet condition on the surface

[0401] 3: The surface is partially wet

[0402] 2: The surface appears wet

[0403] 1: The entire surface is wet.

[0404] 0: Both the front and back surfaces are completely wet

[0405] [Durable water repellency of water- and oil-repellent fiber products]

[0406] The water- and oil-repellent fiber product was washed 10 times (L-10) according to the method of 103 of JIS L0217 (1995), and the water repellency after air-drying was evaluated in the same manner as the above-mentioned water repellency evaluation method.

[0407] [The feel of water- and oil-repellent fiber products]

[0408] The water- and oil-repellent fiber products were evaluated in the following five stages during operation.

[0409] 1: Hard ~ 5: Soft

[0410] Specifically, the feel of the water- and oil-repellent fiber product involved in Example 1 was set as the basis for stage 1, and the feel of the water- and oil-repellent fiber product involved in Example 4 was set as the basis for stage 5. Then, the feel of the water- and oil-repellent fiber products involved in other examples and comparative examples was classified into stages 1 to 5.

[0411] [Evaluation of seam slippage of fiber products]

[0412] The seam slippage resistance of the water- and oil-repellent fiber product was measured according to 8.23 Slippage Resistance 8.23.1 Seam Slippage Method b) Method B of JIS L1096: 2010. A smaller value indicates better seam slippage.

[0413]

[0414] Table 2: Acrylic Dispersion

[0415]

[0416]

[0417]

[0418] Industrial applicability

[0419] The water- and oil-repellent composition of the present invention is excellent in product stability and processing stability, and is useful for the production of water- and oil-repellent products such as water- and oil-repellent fiber products.

Claims

1. A water- and oil-repellent composition comprising a silicone resin, an organic solvent, an emulsifier and an aqueous medium. The organic solvent is an organic solvent in which the amount of water required to dissolve 1 g of the organic solvent at 20° C. exceeds 10 mL. 2 . The water- and oil-repellent composition according to claim 1 , further comprising an amino-modified silicone. The water- and oil-repellent composition according to claim 1 , further comprising an alkyl polysiloxane. The water- and oil-repellent composition according to claim 1 , further comprising a polyfunctional isocyanate.

5. A water- and oil-repellent fiber product, which is obtained by treating the fiber product with the water- and oil-repellent composition according to any one of claims 1 to 4. 6 . A method for producing a water- and oil-repellent fiber product, comprising the step of treating the fiber product with a treatment liquid comprising the water- and oil-repellent composition according to claim 1 .

Images