Surface treatment agent

Abstract

To provide a surface treatment agent that imparts excellent water and oil repellency, especially water repellency, to a base material such as fiber.SOLUTION: Disclosed is a surface treatment agent which contains: (A) a water- and oil-repellent polymer which has a repeating unit derived from at least one water- and oil-repellent monomer that is selected from (A1) fluorine-containing monomers and (A2) non-fluorine monomers having a hydrocarbon group with 7-40 carbon atoms; (B) a silicone polymer represented by formula R533Si-O-[-Si(R51)2-O-]a-[-Si(R51)(R52)-O-]b-SiR533 (wherein R51 represents a hydrogen atom, an alkyl group having 1-20 carbon atoms, an aryl group having 6-20 carbon atoms or an alkoxy group having 1-4 carbon atoms; R52 represents a saturated hydrocarbon group having 23-40 carbon atoms; R53 represents a hydrogen atom, an alkyl group having 1-20 carbon atoms, an aryl group having 6-20 carbon atoms, an alkoxy group having 1-4 carbon atoms or a saturated hydrocarbon group having 23-40 carbon atoms; a represents an integer of 0 or more; b represents an integer of 1 or more; and (a+b) is 10-200); and (C) a liquid medium.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a surface treatment agent comprising a water- and oil-repellent polymer and a silicone polymer. Specifically, the surface treatment agent of the present disclosure can impart excellent water repellency, oil repellency, and stain resistance to textile products (e.g., carpets), paper, nonwoven fabrics, stone materials, electrostatic filters, dust masks, and fuel cell components. [Background technology]

[0002] Fluorine-containing water- and oil-repellent agents containing a fluorine compound have been known in the art, which exhibit good water- and oil-repellency when applied to substrates such as textile products. Recent research results, such as the EPA report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS" (http: / / www.epa.gov / opptintr / pfoa / pfoara.pdf) ], have raised concerns about the environmental impact of PFOA (perfluorooctanoic acid), a type of long-chain fluoroalkyl compound, and on April 14, 2003, the EPA (U.S. Environmental Protection Agency) announced that it would strengthen its scientific investigation of PFOA. On the other hand, the Federal Register (FR Vol.68, No.73 / April 16, 2003[FRL-2303-8], http: / / www.epa.gov / opptintr / pfoa / pfoafr.pdf), EPA Environmental News FOR RELEASE: MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http: / / www.epa.gov / opptintr / pfoa / pfoaprs.pdf) and EPA OPPT FACT SHEET April 14, 2003 (http: / / www.epa.gov / opptintr / pfoa / pfoafacts.pdf) state that telomers may produce PFOA through decomposition or metabolism (telomers refer to long-chain fluoroalkyl groups). It also discloses that telomers are used in many products, including fire foams, care products, cleaning products, carpets, textiles, paper, leather, etc. that have been given water-, oil-, and stain-repellent properties. There is concern that fluorine-containing compounds may accumulate in the environment.

[0003] Patent Document 1 (JP 2017-155095 A) discloses a non-fluorine-based water repellent composition containing a water repellent assistant and a non-fluorine-based water repellent. The organo-modified silicone, which is the water repellent assistant, has a hydrocarbon group having 8 to 40 carbon atoms or an alkyl group having 3 to 22 carbon atoms and an aromatic ring.

[0004] Patent Document 2 (WO 2016 / 048684) discloses a method for imparting water and oil repellency by using a non-fluorinated urethane polymer. Patent Document 3 (WO 2016 / 048642) discloses imparting water repellency by using a polymer formed from a non-fluorinated monomer derived from a sugar alcohol. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2017-155095 A [Patent Document 2] International Publication No. 2016 / 048684 [Patent Document 3] International Publication No. 2016 / 048642 Summary of the Invention [Problem to be solved by the invention]

[0006] One object of the present disclosure is to provide a surface treatment agent (particularly a water repellent agent) that imparts excellent water and oil repellency, particularly water repellency, to a substrate such as a fiber. Another object of the present disclosure is to provide a surface treatment agent that imparts excellent slip resistance to substrates such as fibers. [Means for solving the problem]

[0007] The present disclosure relates to (A) A repeating unit derived from at least one water- and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine-containing monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms. A water- and oil-repellent polymer having the formula: (B) a silicone polymer, and (C) Liquid medium The present invention provides a surface treatment agent comprising: Further, the present disclosure provides (A) A repeating unit derived from at least one water- and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine-containing monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms. An auxiliary used in a surface treatment agent containing a water- and oil-repellent polymer having the formula: An auxiliary comprising the above silicone polymer is provided. In addition, the present disclosure provides (i) a step of polymerizing, in the presence of a liquid medium, a monomer containing at least one water- and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine-containing monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms to obtain an aqueous dispersion of a water- and oil-repellent polymer (A); and (ii) adding a silicone polymer (B) to the aqueous dispersion of the water- and oil-repellent polymer Also provided is a method for producing a surface treatment agent having the formula: Additionally, the present disclosure provides a method of producing a treated substrate comprising applying a surface treatment to a substrate.

[0008] Preferred aspects of the present disclosure are as follows. [1] (A) 30 to 100% by weight of the water- and oil-repellent polymer is a repeating unit derived from at least one water- and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine-containing monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms. A water- and oil-repellent polymer having the formula: Formula (B): (R 53 ) 3 Si-O-[-Si(R 51 ) 2 -O-] a -[-Si(R 51 )(R 52 )-O-] b -Si(R 53 ) 3 [In the formula, R 51 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; R 52 each independently represents a saturated hydrocarbon group having 23 to 40 carbon atoms; R 53 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a saturated hydrocarbon group having 23 to 40 carbon atoms; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 10 to 200. and a silicone polymer represented by the formula: (C) Liquid medium A surface treatment agent comprising:

[0009] [2] the water- and oil-repellent monomer is a fluorine-containing monomer (A1); The fluorine-containing monomer (A1) has the formula: CH 2 =C(-X 11 )-C(=O)-Y 11 -Z 11 -Rf [In the formula, X 11 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 11 is -O- or -NH-, Z 11 is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms.] The surface treatment agent according to [1], which is a compound represented by the following formula:

[0010] [3] In the fluorine-containing monomer (A1), X 11 is a hydrogen atom, a methyl group, or a chlorine atom, and Y 11 is -O- and Z 11 is a direct bond or an alkylene group having 1 to 20 carbon atoms, and Rf is a perfluoroalkyl group. [4] The surface treatment agent according to [2], wherein in the fluorine-containing monomer (A1), Rf has 1 to 6 carbon atoms.

[0011] [5] The surface treatment agent according to [1], wherein the water- and oil-repellent monomer is a non-fluorine-containing monomer (A2). [6] The fluorine-free monomer (A2) is represented by the formula: CH 2 =C(-X)-C(=O)-YR n [In the formula, X is a hydrogen atom, a monovalent organic group, or a halogen atom, Y is a divalent to tetravalent linking group having at least one group selected from -O- and -NH-; R is a hydrocarbon group having 7 to 40 carbon atoms; n is an integer from 1 to 3. The surface treatment agent according to [5], which is a monomer represented by the following formula:

[0012] [7] In the non-fluorine monomer (A2), Y is -Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R' -Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, Y' is a direct bond, -O- or -NH-; R' is -(CH 2 ) m -(m is an integer from 1 to 5) or -C 6 H 6 -(phenylene group). The surface treatment agent according to [6],

[0013] [8] The fluorine-free monomer (A2) is represented by the formula: CH 2 =C(-X 1 )-C(=O)-Y 1 -R 1 [In the formula, X 1 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 1 is -O- or -NH-, R 1 is a hydrocarbon group having 7 to 40 carbon atoms. A compound represented by the formula: CH 2 =C(-X 2 )-C(=O)-Y 2 -Z 1 (-Z 2 -R 2 ) p [In the formula, X 2 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 2 is -O- or -NH-, Z 1 is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, Z 2 each independently represents a divalent to tetravalent linking group having at least one group selected from a direct bond, -O-, and -NH-, R 2 are each independently a hydrocarbon group having 7 to 40 carbon atoms, p is 1 or 2. and compounds of the formula: R 22 -C(=O)-NH-R 23 -OR 21 [In the formula, R 21 represents an organic residue having an ethylenically unsaturated polymerizable group, R 22 is a hydrocarbon group having 7 to 40 carbon atoms, R 23 is a hydrocarbon group having 1 to 5 carbon atoms.] The surface treatment agent according to any one of [1] to [7], wherein the monomer is at least one selected from the group consisting of compounds represented by the following formula:

[0014] [9] The fluorine-containing monomer (A1) is CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -C 6 F 13 CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -C 6 F 13 and CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -C 6 F13 At least one compound selected from the group consisting of The non-fluorinated monomer (A2) is stearyl (meth)acrylate and behenyl (meth)acrylate, Palmitic acid amidoethyl acrylate and stearic acid amidoethyl acrylate, TIFF2025022991000001.tif2044 TIFF2025022991000002.tif2152 TIFF2025022991000003.tif2253 TIFF2025022991000004.tif2153 TIFF2025022991000005.tif2357 TIFF2025022991000006.tif2357 TIFF2025022991000007.tif2361 TIFF2025022991000008.tif2563 TIFF2025022991000009.tif2363 TIFF2025022991000010.tif2966 TIFF2025022991000011.tif3069 [In the above formula, m is an integer of 1 to 5, and n is an integer of 7 to 40], and In the above chemical formula, a methacrylate having a methyl group at the α-position and an acrylate having a chlorine atom at the α-position, The surface treatment agent according to [1], which is at least one compound selected from the group consisting of lauryl (meth)acrylamide, cetyl (meth)acrylamide, stearyl (meth)acrylamide and behenyl (meth)acrylamide.

[0015]

[10] the amount of the water- and oil-repellent polymer (A) is 0.1 to 60% by weight based on the weight of the surface treatment agent; The surface treatment agent according to any one of [1] to [9], wherein the amount of the silicone polymer (B) is 1 to 100 parts by weight per 100 parts by weight of the water- and oil-repellent polymer (A).

[11] The water- and oil-repellent polymer is (A3) a repeating unit derived from a non-fluorine-containing non-crosslinkable monomer, and (A4) Repeating unit derived from a non-fluorinated crosslinkable monomer The surface treatment agent according to any one of [1] to

[10] , further comprising at least one selected from the group consisting of:

[0016]

[12] the fluorine-free non-crosslinkable monomer (A3) is at least one compound selected from the group consisting of vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, vinylidene bromide, and vinylidene iodide; The surface treatment agent according to

[11] , wherein the non-fluorine-containing crosslinkable monomer (A4) is at least one compound selected from the group consisting of diacetone acrylamide, (meth)acrylamide, N-methylol acrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, butadiene, isoprene, chloroprene, and glycidyl (meth)acrylate.

[0017]

[13] In silicone polymers, R 51 and R 53 The surface treatment agent according to any one of [1] to

[12] , wherein the alkyl group is not an alkyl group having 3 to 22 carbon atoms.

[14] In silicone polymers, R 51 and R 53 Each of the radicals R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24,

[0018]

[15] the amount of the water- and oil-repellent monomer is 32 to 98% by weight based on the water- and oil-repellent polymer (A); the amount of the non-fluorine-containing non-crosslinkable monomer (A3) is 2 to 68% by weight based on the water- and oil-repellent polymer, The surface treatment agent according to

[11] or

[12] , wherein the amount of the non-fluorine-crosslinkable monomer (A4) is 50 parts by weight or less based on 100 parts by weight of the water- and oil-repellent monomer.

[0019]

[16] The surface treatment agent according to any one of [1] to

[13] , which is a water / oil repellent, an antifouling agent or a dirt release agent.

[17] (A) 30 to 100% by weight of the water- and oil-repellent polymer is a repeating unit derived from at least one water- and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine-containing monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms. An auxiliary used in a surface treatment agent containing a water- and oil-repellent polymer having the formula: Formula (B): (R 53 ) 3 Si-O-[-Si(R 51 ) 2 -O-] a -[-Si(R 51 )(R 52 )-O-] b -Si(R 53 ) 3 [In the formula, R 51 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; R 52 each independently represents a saturated hydrocarbon group having 23 to 40 carbon atoms; R 53 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a saturated hydrocarbon group having 23 to 40 carbon atoms; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 10 to 200. The auxiliary comprises a silicone polymer represented by the formula:

[0020]

[18] Formula (B): (R 53 ) 3 Si-O-[-Si(R 51 ) 2 -O-] a -[-Si(R 51 )(R 52 )-O-] b -Si(R 53 ) 3 [In the formula, R 51 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; R 52 each independently represents a saturated hydrocarbon group having 23 to 40 carbon atoms; R 53 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a saturated hydrocarbon group having 23 to 40 carbon atoms; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 10 to 200. Use of a silicone polymer represented by the formula: The auxiliary comprises repeating units derived from at least one water- and oil-repellent monomer selected from the group consisting of a fluorine-containing monomer (A1) and a non-fluorine-containing monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms, in an amount of 30 to 100% by weight based on the water- and oil-repellent polymer (A). The use in a surface treatment agent comprising a water- and oil-repellent polymer having the formula:

[0021]

[19] (i) a step of polymerizing, in the presence of a liquid medium, a monomer containing at least one water- and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine-containing monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms to obtain an aqueous dispersion of a water- and oil-repellent polymer (A) having a repeating unit derived from the water- and oil-repellent monomer in an amount of 30 to 100% by weight based on the water- and oil-repellent polymer; (ii) adding a silicone polymer (B) to the aqueous dispersion of the water- and oil-repellent polymer The method for producing the surface treatment agent according to any one of [1] to

[16] ,

[20] A method for producing a treated substrate, comprising applying the surface treatment agent according to any one of [1] to

[16] to a substrate. Effect of the Invention

[0022] The surface treatment agent of the present disclosure does not cause particle settling and does not cause the polymer to adhere to the roll and stain the fabric. According to the present disclosure, excellent water repellency, oil repellency, stain resistance and stain release properties, particularly water repellency, can be obtained. The water repellency, oil repellency, stain resistance and stain release properties are excellent in durability. The surface treatment agent of the present disclosure imparts excellent slip resistance (excellent resistance to sliding off) to a substrate. The surface treatment agent of the present disclosure can be used as a water / oil repellent, an antifouling agent and / or a soil release agent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The surface treatment agent is generally an aqueous emulsion or an organic solvent solution containing a water- and oil-repellent polymer and a silicone polymer. The surface treatment agent is (A) a water- and oil-repellent polymer having a repeating unit derived from a water- and oil-repellent monomer which is either or both of a fluorine-containing monomer (A1) having a fluoroalkyl group or a non-fluorine-containing monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms (i.e., a long-chain hydrocarbon group-containing non-fluorine-containing monomer); (B) a silicone polymer, and (C) Liquid medium The present invention relates to a method for producing a semiconductor device comprising the steps of:

[0024] (A) Water- and oil-repellent polymer The water- and oil-repellent polymer is a homopolymer having a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group or a non-fluorine-containing monomer having a hydrocarbon group having 7 to 40 carbon atoms (i.e., a long-chain hydrocarbon group-containing non-fluorine-containing monomer), a copolymer having a repeating unit derived from two or more monomers selected from a fluorine-containing monomer having a fluoroalkyl group and a long-chain hydrocarbon group-containing non-fluorine-containing monomer, or a copolymer having a repeating unit derived from another polymerizable compound copolymerizable with the repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group or a long-chain hydrocarbon group-containing non-fluorine-containing monomer. The water- and oil-repellent polymer is a fluorine-containing polymer or a non-fluorine-containing polymer that does not have fluorine atoms. The fluorine-containing polymer is a polymer having a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group, and the non-fluorine-containing polymer is a polymer having a repeating unit derived from a non-fluorine-containing monomer containing a long-chain hydrocarbon group. The water- and oil-repellent polymer may be a random polymer or a block polymer.

[0025] In the present disclosure, the water- and oil-repellent polymer (A) may consist only of (A1) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group and / or (A2) a repeating unit derived from a non-fluorine-containing monomer containing a long-chain hydrocarbon group, In addition to the repeating units (A1) and / or (A2), (A3) a repeating unit derived from a non-fluorine-containing non-crosslinkable monomer and / or (A4) a repeating unit derived from a non-fluorine-containing crosslinkable monomer It is preferred that the compound has the formula:

[0026] The water- and oil-repellent polymer (A) has repeating units derived from one or both of (A1) a fluorine-containing monomer having a fluoroalkyl group and (A2) a non-fluorine-containing monomer having a long chain hydrocarbon group. That is, the water- and oil-repellent polymer (A) has repeating units derived from (A1) a fluorine-containing monomer having a fluoroalkyl group and (A2) a non-fluorine-containing monomer having a long chain hydrocarbon group.

[0027] (A1) Fluorine-containing monomer The fluorine-containing monomer is generally a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group, a methacrylic acid group or an α-substituted acrylic acid group.

[0028] The fluorine-containing monomer (A1) has the formula: CH 2 =C(-X 11 )-C(=O)-Y 11 -Z 11 -Rf [In the formula, X 11 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 11 is -O- or -NH-, Z 11 is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms.] It is preferable that the compound is represented by the following formula:

[0029] Z 11 is, for example, a linear or branched aliphatic group having 1 to 20 carbon atoms (particularly, an alkylene group), for example, a group represented by the formula -(CH 2 ) x - (wherein x is 1 to 10), or a group represented by the formula -R 2 (R 1 )N-SO 2 - or formula -R 2 (R 1 ) a group represented by N—CO— (wherein, R 1 is an alkyl group having 1 to 10 carbon atoms, and R 2is a straight chain or branched alkylene group having 1 to 10 carbon atoms; or 2 CH(OR 3 )CH 2 -(Ar-O) p -(In the formula, R 3 represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms (such as formyl or acetyl), Ar represents an arylene group optionally having a substituent, and p represents 0 or 1, or a group represented by the formula -CH 2 -Ar-(O) q - (wherein Ar is an arylene group optionally having a substituent, and q is 0 or 1), a group represented by -(CH 2 ) m -SO 2 -(CH 2 ) n - group or -(CH 2 ) m -S-(CH 2 ) n -group (wherein m is 1 to 10, and n is 0 to 10). X 11 Examples of this are H, CH 3 , Cl, Br, I, F, CN, CF 3 X 11 is preferably a methyl group or a chlorine atom, and particularly preferably a chlorine atom.

[0030] The fluorine-containing monomer has the general formula: CH 2 =C(-X 11 )-C(=O)-Y 11 -Z 11 -Rf [In the formula, X 11 is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, CFX 1 X 2 Group (where X 1 and X 2is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group; Y 11 is -O- or -NH-; Z 11 is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms, -CH 2 CH 2 N(R 1 )SO 2 - group (wherein R 1 is an alkyl group having 1 to 4 carbon atoms. -CH 2 CH(OZ 1 )CH 2 -(Ph-O) p - group (wherein Z 1 is a hydrogen atom or an acetyl group, Ph is a phenylene group, and p is 0 or 1. ), -(CH 2 ) n -Ph-O- group (wherein Ph is a phenylene group and n is 0 to 10), -(CH 2 ) m -SO 2 -(CH 2 ) n - group or -(CH 2 ) m -S-(CH 2 ) n - group (wherein m is 1 to 10 and n is 0 to 10), Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms.] It is preferable that the acrylate ester or acrylamide is represented by the following formula:

[0031] In the fluorine-containing monomer, the Rf group is preferably a perfluoroalkyl group. The number of carbon atoms in the Rf group is preferably 1 to 12, for example 1 to 6, particularly 4 to 6, and especially 6. Examples of the Rf group include -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF3 , -CF(CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF(CF 3 ) 2 , -C(CF 3 ) 3 , -(CF 2 ) 4 CF 3 , -(CF 2 ) 2 CF(CF 3 ) 2 , -CF 2 C(CF 3 ) 3 , -CF(CF 3 )CF 2 CF 2 CF 3 , -(CF 2 ) 5 CF 3 , -(CF 2 ) 3 CF(CF 3 ) 2 , -(CF 2 ) 4 CF(CF 3 ) 2 , -C 8 F 17 etc.

[0032] Z 11 represents an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms, -CH 2 CH 2 N(R 1 )SO 2 - group (wherein R 1 is an alkyl group having 1 to 4 carbon atoms. -CH 2 CH(OZ 1 )CH 2 -(Ph-O) p - group (wherein Z 1 is a hydrogen atom or an acetyl group, Ph is a phenylene group, and p is 0 or 1. ), -(CH 2 ) n-Ph-O- group (wherein Ph is a phenylene group and n is 0 to 10), -(CH 2 ) m -SO 2 -(CH 2 ) n - group or -(CH 2 ) m -S-(CH 2 ) n - group (wherein m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (particularly having 1 to 4 carbon atoms, for example 1 or 2). The aromatic group or cyclic aliphatic group may be substituted or unsubstituted. S group or SO 2 The group may be directly attached to the Rf group.

[0033] Specific examples of the fluorine-containing monomer include, but are not limited to, the following: CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -Rf CH 2 =C(-H)-C(=O)-OC 6 H 4 -Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 N(-CH 3 ) SO 2 -Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 N(-C 2 H 5 ) SO 2 -Rf CH 2 =C(-H)-C(=O)-O-CH 2 CH(-OH)CH 2 -Rf

[0034] CH 2 =C(-H)-C(=O)-O-CH 2 CH(-OCOCH 3 ) CH 2 -Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-H)-C(=O)-NH-(CH 2 ) 2 -Rf CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -SO 2-(CH 2 ) 2 -Rf CH 2 =C(-CH 3 )-C(=O)-NH-(CH 2 ) 2 -Rf

[0035] CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-F)-C(=O)-NH-(CH 2 ) 2 -Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -SO 2-(CH 2 ) 2 -Rf CH 2 =C(-Cl)-C(=O)-NH-(CH 2 ) 2 -Rf

[0036] CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-CF 3 )-C(=O)-NH-(CH 2 ) 2 -Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-CF 2 H )-C(=O)-O-(CH 2 ) 2 -SO2 -Rf CH 2 =C(-CF 2 H )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-CF 2 H )-C(=O)-NH-(CH 2 ) 2 -Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-CN )-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf CH 2 =C(-CN )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-CN )-C(=O)-NH-(CH 2 ) 2 -Rf

[0037] CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-NH-(CH 2 ) 2 -Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -S-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-F)-C(=O)-NH-(CH 2 ) 3 -Rf

[0038] CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -S-Rf CH 2=C(-Cl)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -S-Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -S-Rf CH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf CH 2=C(-CF 2 H )-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-CF 2 H )-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf

[0039] CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -S-Rf CH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf CH 2 =C(-CN )-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-CN )-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 3 -S-Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 3-SO 2 -Rf CH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf [In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms.]

[0040] (A2) Fluorine-free monomer containing a long-chain hydrocarbon group The long-chain hydrocarbon group-containing non-fluorine-containing monomer does not have a fluoroalkyl group.The long-chain hydrocarbon group-containing non-fluorine-containing monomer does not contain a fluorine atom. The long-chain hydrocarbon group may be a saturated or unsaturated group, and is preferably a saturated hydrocarbon group, particularly preferably an alkyl group.

[0041] The long chain hydrocarbon group is preferably a linear or branched hydrocarbon group having 7 to 40 carbon atoms. The linear or branched hydrocarbon group may have 10 to 40, 12 to 40, or 18 to 40 carbon atoms. The linear or branched hydrocarbon group preferably has 12 to 40 carbon atoms, more preferably 12 to 30, particularly 18 to 28, and especially 18 to 22 (or 18 to 24), and is generally preferably a saturated aliphatic hydrocarbon group, particularly an alkyl group. The long chain hydrocarbon group is particularly preferably a stearyl group, an icosyl group, or a behenyl group.

[0042] The long chain hydrocarbon group-containing non-fluorine-containing monomer has the formula: CH 2 =C(-X)-C(=O)-YR n [In the formula, X is a hydrogen atom, a monovalent organic group, or a halogen atom, Y is a divalent to tetravalent linking group having at least one group selected from -O- and -NH-; R is a hydrocarbon group having 7 to 40 carbon atoms; n is an integer from 1 to 3. It is preferable that the monomer is a monomer represented by the following formula:

[0043] X may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. X is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0044] Y is a divalent to tetravalent group. Y is preferably a divalent group. Y is a hydrocarbon group having one carbon atom, -C 6 H 6 -, -O-, -C(=O)-, -S(C=O) 2 - or -NH- (excluding hydrocarbon groups). An example of a hydrocarbon group having one carbon atom is -CH 2 -, -CH= or -C≡.

[0045] Examples of Y are -Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R' -Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, Y' is a direct bond, -O- or -NH-; R' is -(CH 2 ) m -(m is an integer from 1 to 5) or -C 6 H 6 -(phenylene group). It is.

[0046] Specific examples of Y include -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -OC 6 H 6 -, -O-(CH 2 ) m-O-, -NH-(CH 2 ) m -NH-, -O-(CH 2 ) m -NH-, -NH-(CH 2 ) m -O-, -O-(CH 2 ) m -O-C(=O)-, -O-(CH 2 ) m -C(=O)-O-, -NH-(CH 2 ) m -O-C(=O)-, -NH-(CH 2 ) m -C(=O)-O-, -O-(CH 2 ) m -O-C(=O)-NH-, -O-(CH 2 ) m -NH-C(=O)-O-, -O-(CH 2 ) m -C(=O)-NH-, -O-(CH 2 ) m -NH-C(=O)-, -O-(CH 2 ) m -NH-C(=O)-NH-, -O-(CH 2 ) m -O-C 6 H 6 -, -NH-(CH 2 ) m -O-C(=O)-NH-, -NH-(CH 2 ) m -NH-C(=O)-O-, -NH-(CH 2 ) m -C(=O)-NH-, -NH-(CH 2 ) m -NH-C(=O)-, -NH-(CH 2 ) m -NH-C(=O)-NH-, -NH-(CH 2 ) m -O-C 6 H 6 -, -NH-(CH 2 ) m -NH-C 6 H 6 - [In the formula, m is an integer of 1 to 5, particularly 2 or 4.] Examples include:

[0047] Y is -O-, -NH-, -O-(CH 2 ) m -OC(=O)-, -O-(CH 2 ) m -NH-C(=O)-, -O-(CH 2 ) m -OC(=O)-NH-, -O-(CH 2 ) m -NH-C(=O)-O-, -O-(CH 2 ) m -NH-C(=O)-NH- [In the formula, m is an integer of 1 to 5, particularly 2 or 4.] More preferably, Y is -O-(CH 2 ) m It is particularly preferred that the group is --NH--C(.dbd.O)--.

[0048] Y is -O-, -NH-, -O-(CH 2 ) m -NH-C(=O)-, -O-(CH 2 ) m -OC(=O)-NH-, -O-(CH 2 ) m -NH-C(=O)-O-, -O-(CH 2 ) m -NH-C(=O)-NH- [In the formula, m is an integer of 1 to 5, particularly 2 or 4.] It is particularly preferred that:

[0049] R is preferably a linear or branched hydrocarbon group. The hydrocarbon group may be, in particular, a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, in particular a saturated aliphatic hydrocarbon group, especially an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26, in particular 18 to 22.

[0050] n is an integer of 1 to 3, preferably 1. When Y has a tetravalent hydrocarbon group having 1 carbon atom, n is preferably 3. When Y has a trivalent hydrocarbon group having 1 carbon atom, n is preferably 2. When Y has neither a trivalent nor a tetravalent hydrocarbon group having 1 carbon atom, n is 1.

[0051] Examples of the long-chain hydrocarbon group-containing non-fluorinated monomer (A2) are (a1) an acrylic monomer in which C(=O)-O- or C(=O)-NH- is directly bonded to a hydrocarbon group having 7 to 40 carbon atoms, and (a2) It is an acrylic monomer in which C(=O)-O- or C(=O)-NH- is not directly bonded to a hydrocarbon group having 7 to 40 carbon atoms.

[0052] The acrylic monomer (a2) is a compound different from the acrylic monomer (a1). The acrylic monomer (a2) may be a (meth)acrylate or (meth)acrylamide having an amide group, a urethane group or a urea group (which is not directly bonded to C(=O)-O- or C(=O)-NH-, but is directly bonded to a hydrocarbon group having 7 to 40 carbon atoms). The nitrogen-containing monomer is preferably an acrylate having an amide group which is not directly bonded to C(=O)-O- or C(=O)-NH-, but is directly bonded to a hydrocarbon group having 7 to 40 carbon atoms.

[0053] (a1) Acrylic monomer The acrylic monomer (a1) is represented by the formula: CH 2 =C(-X 1 )-C(=O)-Y 1 -R 1 [In the formula, X 1 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 1 is -O- or -NH-, R 1 is a hydrocarbon group having 7 to 40 carbon atoms. It is preferable that the compound is represented by the following formula:

[0054] The acrylic monomer (a1) is Y 1 a long chain acrylate ester monomer in which Y is -O-; or 1 is a long chain acrylamide monomer in which is -NH-.

[0055] X 1 X may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. 1 Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. 1 is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0056] Y 1 is -O- or -NH-.

[0057] R is preferably a linear or branched hydrocarbon group. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26, particularly 18 to 22 (or 18 to 24).

[0058] Specific examples of long chain acrylate ester monomers are lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha chloroacrylate, icosyl alpha chloroacrylate, behenyl alpha chloroacrylate. Specific examples of long chain acrylamide monomers are lauryl (meth)acrylamide, stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide. The presence of the long chain acrylate ester monomer or long chain acrylamide monomer enhances the water and oil repellency and hand quality imparted by the water and oil repellent polymer.

[0059] (a2) Acrylic monomer The acrylic monomer (a2) may be a (meth)acrylate or (meth)acrylamide having a divalent to tetravalent linking group having at least one group selected from -O- and -NH- between C(=O)-O- or C(=O)-NH- and a hydrocarbon group having 7 to 40 carbon atoms. The acrylic monomer (a2) is represented by the formula: CH 2 =C(-X 2 )-C(=O)-Y 2 -Z 1 (-Z 2 -R 2 ) p [In the formula, X 2 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 2 is -O- or -NH-, Z 1 is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, Z 2 each independently represents a divalent to tetravalent linking group having at least one group selected from a direct bond, -O-, and -NH-, R 2 are each independently a hydrocarbon group having 7 to 40 carbon atoms, p is 1 or 2. It is preferable that the compound is represented by the following formula:

[0060] The acrylic monomer (a2) is Y 2 a long chain acrylate ester monomer in which Y is -O-; or 2 is a long chain acrylamide monomer in which is -NH-.

[0061] X 2 X may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. 2 Examples of X are hydrogen, methyl, chlorine, bromine, iodine, and cyano. The less rigid the main chain of the resulting polymer, the less the crystallinity of the side chains is hindered. 2is preferably a hydrogen atom, a methyl group, or a chlorine atom, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0062] Y 2 is -O- or -NH-.

[0063] Z 1 Z is a direct bond or a divalent or trivalent hydrocarbon group (particularly an alkyl group) having 1 to 5 carbon atoms, and may have a branched structure. 1 The carbon number of Z is preferably 2 to 4, and particularly preferably 2. 1 Specific examples of the divalent group include a direct bond and -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 -, -CH having a branched structure (a trivalent group) 2 CH=, -CH 2 (CH-)CH 2 -, -CH 2 CH 2 CH=, -CH 2 CH 2 CH 2 CH 2 CH=, -CH 2 CH 2 (CH-)CH 2 -, -CH 2 CH 2 CH 2 CH=Z 1 is preferably not a direct bond.

[0064] Z 2 Specific examples of the group include a direct bond, -O-, -NH-, -(O) k-C(=O)-、-C(=O)-O-、-C(=O)-NH-、-NH-C(=O)-、-(O) k -C(=O)-NH-、-NH-C(=O)-O-、-NH-C(=O)-NH-、-(O) k -C 6 H 6 -、-(O) k -(CH 2 ) m -O-、-NH-(CH 2 ) m -GRAPE) k -(CH 2 ) m -NH-、-NH-(CH 2 ) m -O-、-(O) k -(CH 2 ) m -OC(=O)-、-(O) k -(CH 2 ) m -C(=O)-O-、-NH-(CH 2 ) m -OC(=O)-、-NH-(CH 2 ) m -C(=O)-O-、-(O) k -(CH 2 ) m -OC(=O)-NH-、-(O) k -(CH 2 ) m -NH-C(=O)-O-、-(O) k -(CH 2 ) m -C(=O)-NH-、-(O) k -(CH 2 ) m -NH-C(=O)-、-(O) k -(CH 2 ) m -NH-C(=O)-NH-、-(O) k -(CH 2 ) m -OC 6 H 6 -、-NH-(CH 2 ) m -OC(=O)-NH-、-NH-(CH 2 ) m-NH-C(=O)-O-, -NH-(CH 2 ) m -C(=O)-NH-, -NH-(CH 2 ) m -NH-C(=O)-, -NH-(CH 2 ) m -NH-C(=O)-NH-, -NH-(CH 2 ) m -OC 6 H 6 -, -NH-(CH 2 ) m -NH-C 6 H 6 - in which k is 0 or 1, and m is an integer of 1 to 5, particularly 2 or 4.

[0065] Z 2 is -(O) k -, -NH-, -(O) k -(CH 2 ) m -OC(=O)-, -(O) k -(CH 2 ) m -NH-C(=O)-, -(O) k -(CH 2 ) m -OC(=O)-NH-, -(O) k -(CH 2 ) m -NH-C(=O)-O-, -(O) k -(CH 2 ) m -NH-C(=O)-NH- [In the formula, k is 0 or 1, and m is an integer of 1 to 5, particularly 2 or 4.] It is particularly preferred that:

[0066] Z 1 and Z 2 cannot simultaneously be a direct bond.

[0067] R 2is preferably a linear or branched hydrocarbon group. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The carbon number of the hydrocarbon group is preferably 12 to 30, for example 16 to 26, particularly 18 to 22 (or 18 to 24).

[0068] The acrylic monomer (a2) is CH 2 =C(-X 2 )-C(=O)-O-(CH 2 ) m -NH-C(=O)-R 2 , C.H. 2 =C(-X 2 )-C(=O)-OR 2 or a combination thereof is preferable, [wherein X 2 , m and R 2 has the same meaning as above.]. The acrylic monomer (a2) is CH 2 =C(-X 2 )-C(=O)-O-(CH 2 ) m -NH-C(=O)-R 2 It is particularly preferred that:

[0069] The acrylic monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or a hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate, such as lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, or behenyl isocyanate. Alternatively, the acrylic monomer (a2) can be produced by reacting a (meth)acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl isocyanate, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0070] Specific examples of the acrylic monomer (a2) are as follows: The compound of the following chemical formula is an acrylate having a hydrogen atom at the α-position, but specific examples may be a methacrylate having a methyl group at the α-position and an acrylate having a chlorine atom at the α-position. TIFF2025022991000012.tif2044

[0071] TIFF2025022991000013.tif2152 TIFF2025022991000014.tif2253 TIFF2025022991000015.tif2153

[0072] TIFF2025022991000016.tif2357 TIFF2025022991000017.tif2357 TIFF2025022991000018.tif2361

[0073] TIFF2025022991000019.tif2563 TIFF2025022991000020.tif2363

[0074] TIFF2025022991000021.tif2966 TIFF2025022991000022.tif3069 [In the above formula, m is an integer of 1 to 5, and n is an integer of 7 to 40], and In the above chemical formula, methacrylate has a methyl group at the α-position and acrylate has a chlorine atom at the α-position.

[0075] Representative examples of the acrylic monomer (a2) include palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, behenic acid amidoethyl (meth)acrylate, and myristate amidoethyl (meth)acrylate.

[0076] The acrylic monomer (a2) is represented by the formula: R 22 -C(=O)-NH-R 23 -OR 21 [In the formula, R 21 represents an organic residue having an ethylenically unsaturated polymerizable group, R 22 is a hydrocarbon group having 7 to 40 carbon atoms, R 23 is a hydrocarbon group having 1 to 5 carbon atoms.] Particularly preferred is an amide group-containing monomer represented by the following formula:

[0077] R 21 is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a carbon-carbon double bond. 24 =CH 2 , -CHR 24 =CH 2 , -CH 2 CHR 24 =CH 2 Examples of organic residues having an ethylenically unsaturated polymerizable group include R 24 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 21 R may have various organic groups other than the ethylenically unsaturated polymerizable group, such as an organic group of a chain hydrocarbon, a cyclic hydrocarbon, a polyoxyalkylene group, a polysiloxane group, etc., and these organic groups may be substituted with various substituents. 21is -C(=O)CR 24 =CH 2 It is preferable that: R 22 R is a hydrocarbon group having 7 to 40 carbon atoms, preferably an alkyl group, and examples thereof include chain hydrocarbons and cyclic hydrocarbons. Among these, chain hydrocarbons are preferred, and linear saturated hydrocarbon groups are particularly preferred. 21 The number of carbon atoms is 7 to 40, preferably 11 to 27, and particularly preferably 15 to 23. R 23 R is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched and may have an unsaturated bond, but is preferably linear. 23 The number of carbon atoms in R is preferably 2 to 4, and more preferably 2. 23 is preferably an alkylene group.

[0078] The amide group-containing monomer is R 21 is alone (e.g., R 21 (Only compounds with 17 carbon atoms) or R 21 is a combination of multiple 21 A compound having 17 carbon atoms, R 21 and a compound having 15 carbon atoms.

[0079] An example of an amide group-containing monomer is a carboxylic acid amide alkyl (meth)acrylate. Specific examples of amide group-containing monomers include palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, behenic acid amidoethyl (meth)acrylate, myristic acid amidoethyl (meth)acrylate, lauric acid amidoethyl (meth)acrylate, isostearic acid ethyl amido (meth)acrylate, oleic acid ethyl amido (meth)acrylate, tertiary butyl cyclohexyl caproic acid amidoethyl (meth)acrylate, adamantane carboxylic acid ethyl amido (meth)acrylate, naphthalene carboxylic acid amidoethyl (meth)acrylate, anthracene carboxylic acid amidoethyl (meth)acrylate, palmitic acid amidopropyl (meth)acrylate, stearic acid amidopropyl (meth)acrylate, palmitic acid amidoethyl vinyl ether, stearic acid amidoethyl vinyl ether, palmitic acid amidoethyl allyl ether, stearic acid amidoethyl allyl ether, or mixtures thereof.

[0080] The amide group-containing monomer is preferably stearamidoethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamidoethyl (meth)acrylate. In the mixture containing stearamidoethyl (meth)acrylate, the amount of stearamidoethyl (meth)acrylate may be, for example, 55 to 99% by weight, preferably 60 to 85% by weight, more preferably 65 to 80% by weight, based on the total weight of the amide group-containing monomer, and the remaining monomer may be, for example, palmitamidoethyl (meth)acrylate.

[0081] (A3) Fluorine-free non-crosslinkable monomer The non-fluorine non-crosslinkable monomer (A3) is a monomer other than the long-chain hydrocarbon group-containing non-fluorine monomer (A2). The non-fluorine non-crosslinkable monomer (A3) is a monomer that does not contain a fluorine atom. The non-fluorine non-crosslinkable monomer (A3) does not have a crosslinkable functional group. The non-fluorine non-crosslinkable monomer (A3) is non-crosslinkable, unlike the crosslinkable monomer (A4). The non-fluorine non-crosslinkable monomer (A3) is preferably a non-fluorine monomer having an ethylenically unsaturated carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (A3) is preferably a vinyl monomer that does not contain fluorine. The non-fluorine non-crosslinkable monomer (A3) is generally a compound having one ethylenically unsaturated carbon-carbon double bond.

[0082] A preferred fluorine-free non-crosslinkable monomer (A3) is represented by the formula: CH 2 =CA-T [In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom, or an iodine atom), T is a hydrogen atom, a linear or cyclic hydrocarbon group having 1 to 40 carbon atoms, or a linear or cyclic organic group having 1 to 41 carbon atoms and an ester bond.] It is a compound represented by the formula:

[0083] Examples of the linear or cyclic hydrocarbon group having 1 to 40 carbon atoms include linear or branched aliphatic hydrocarbon groups having 1 to 40 carbon atoms, cyclic aliphatic groups having 4 to 40 carbon atoms, aromatic hydrocarbon groups having 6 to 40 carbon atoms, and aromatic aliphatic hydrocarbon groups having 7 to 40 carbon atoms.

[0084] Examples of the linear or cyclic organic group having 1 to 41 carbon atoms and an ester bond include -C(=O)-OQ and -OC(=O)-Q (wherein Q is a linear or branched aliphatic hydrocarbon group having 1 to 40 carbon atoms, a cyclic aliphatic group having 4 to 40 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 40 carbon atoms).

[0085] Preferred examples of the non-fluorine non-crosslinkable monomer (A3) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and vinyl alkyl ether. The non-fluorine non-crosslinkable monomer (A3) is not limited to these examples.

[0086] The non-fluorine-containing non-crosslinkable monomer (A3) may be a (meth)acrylate ester having an alkyl group. The alkyl group may have 1 to 17 carbon atoms. For example, the non-fluorine-containing non-crosslinkable monomer (A3) may be a (meth)acrylate ester having an alkyl group. CH 2 =CA 1 COOA 2 [In the formula, A 1 is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom, or an iodine atom), A 2 is C n H 2n+1 (n=1 to 17).] The acrylate may be represented by the formula: The fluorine-containing monomer does not necessarily have to have a repeating unit derived from a (meth)acrylate ester having an alkyl group having 1 to 17 carbon atoms.

[0087] The non-fluorine-containing non-crosslinkable monomer (A3) may be a (meth)acrylate monomer having a cyclic hydrocarbon group. The (meth)acrylate monomer having a cyclic hydrocarbon group is a compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth)acrylate group. The monovalent cyclic hydrocarbon group and the monovalent (meth)acrylate group are directly bonded. Examples of the cyclic hydrocarbon group include a monocyclic group, a polycyclic group, and a bridged ring group, which are saturated or unsaturated. The cyclic hydrocarbon group is preferably saturated. The number of carbon atoms in the cyclic hydrocarbon group is preferably 4 to 20. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an aromatic aliphatic group having 7 to 20 carbon atoms. The number of carbon atoms in the cyclic hydrocarbon group is particularly preferably 15 or less, for example 10 or less. It is preferable that a carbon atom in the ring of the cyclic hydrocarbon group is directly bonded to an ester group in the (meth)acrylate group. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group.

[0088] Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an adamantyl group. The acrylate group is preferably an acrylate group or a methacrylate group, and is particularly preferably a methacrylate group. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate.

[0089] The non-fluorine-containing non-crosslinkable monomer (A3) may be a halogenated olefin. The halogenated olefin may be a halogenated olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly a 2 to 5 carbon atom olefin having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin include vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, and vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide.

[0090] (A4) Fluorine-free crosslinkable monomer The water- and oil-repellent polymer may have a repeating unit derived from a non-fluorine crosslinkable monomer (A4). The non-fluorine crosslinkable monomer (A4) is a monomer that does not contain a fluorine atom. The non-fluorine crosslinkable monomer (A4) may be a compound having at least two reactive groups and / or ethylenically unsaturated carbon-carbon double bonds and not containing fluorine. The non-fluorine crosslinkable monomer (A4) may be a compound having at least two ethylenically unsaturated carbon-carbon double bonds, or a compound having at least one ethylenically unsaturated carbon-carbon double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, and the like.

[0091] Examples of the non-fluorine-containing crosslinkable monomer (A4) include, but are not limited to, diacetone acrylamide, (meth)acrylamide, N-methylol acrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, butadiene, isoprene, chloroprene, and glycidyl (meth)acrylate.

[0092] By copolymerizing the non-fluorine-free non-crosslinkable monomer (A3) and / or the non-fluorine-free crosslinkable monomer (A4), various properties such as water- and oil-repellency and soil resistance, as well as cleaning resistance, washing resistance, solubility in solvents, hardness, and feel of the resin can be improved as required.

[0093] The monomer may be polymerized in the presence of at least one compound selected from the group consisting of a blocked isocyanate compound and an organopolysiloxane compound. The amount of the blocked isocyanate compound (or the organopolysiloxane compound) may be 0 to 100 parts by weight, for example, 1 to 50 parts by weight, based on 100 parts by weight of the monomer.

[0094] A polymer having a blocked isocyanate group is obtained by polymerizing a monomer in the presence of a blocked isocyanate compound. The blocked isocyanate compound is an isocyanate blocked with at least one blocking agent. Examples of blocking agents include oximes, phenols, alcohols, mercaptans, amides, imides, imidazoles, ureas, amines, imines, pyrazoles, and active methylene compounds. Other examples of blocking agents include pyridinols, thiophenols, diketones, and esters. The blocked isocyanate compound may be modified with a compound having a hydrophilic group.

[0095] The monomers are polymerized in the presence of an organopolysiloxane compound (e.g., a mercapto-functional organopolysiloxane, a vinyl-functional organopolysiloxane) to obtain a polymer having siloxane groups. In one embodiment, the mercapto-functional organopolysiloxane has siloxy units having the average formula: (R 2 SiO) a (RR N SiO) b (RR S SiO) c [In the formula, a represents 0 to 4000, alternatively 0 to 1000, alternatively 0 to 400, b is 1 to 1000, or 1 to 100, or 1 to 50; c is 1 to 1000, alternatively 1 to 100, alternatively 1 to 50; R is independently a monovalent organic group; Alternatively, R is a hydrocarbon having 1 to 40 carbon atoms; Alternatively, R is a monovalent alkyl group having 1 to 12 carbon atoms; Alternatively, R is a methyl group; R N is a monovalent amino-functional organic group, R S is a monovalent mercapto-functional organic group.

[0096] Particularly preferred combinations of monomers in the water- and oil-repellent polymer are as follows. Fluorine-containing monomer (A1) + non-fluorine-containing monomer (A2) (particularly, long-chain (meth)acrylate ester monomer (A2-i)), Long-chain (meth)acrylate ester monomer (A2-i) + amide group-containing monomer (A2-ii) Long-chain (meth)acrylate ester monomer (A2-i) + nitrogen-containing monomer (A2-iii) Long chain (meth)acrylate ester monomer (A2-i) + acrylamide monomer (A2-iv) The above combination preferably further contains a halogenated olefin.

[0097] The amount of each of the fluorine-containing monomer (A1) and the long-chain hydrocarbon group-containing non-fluorine monomer (A2) (or the total of the monomer (A1) and the monomer (A2)) (provided that the total of the monomer (A1) and the monomer (A2) is 100% by weight or less) may be 30 to 100% by weight, preferably 32 to 98% by weight, for example 35 to 95% by weight, and particularly 40 to 90% by weight, based on the water- and oil-repellent polymer. In the water- and oil-repellent polymer, for a total of 100 parts by weight of the fluorine-containing monomer (A1) and the long-chain hydrocarbon group-containing non-fluorine-containing monomer (A2), the amount of the non-fluorine-containing non-crosslinkable monomer (A3) is 1000 parts by weight or less, for example, 0.1 to 300 parts by weight, particularly 1 to 200 parts by weight; The amount of the non-fluorine crosslinkable monomer (A4) may be 50 parts by weight or less, for example 30 parts by weight or less, particularly from 0.1 to 20 parts by weight. The amount of the non-fluorine-containing non-crosslinkable monomer (A3) may be 2 to 68% by weight, for example 5 to 65% by weight, and particularly 10 to 60% by weight, based on the water- and oil-repellent polymer (or the total of the monomer (A1), the monomer (A2) and the monomer (A3)).

[0098] The number average molecular weight (Mn) of the water- and oil-repellent polymer may generally be 1,000 to 1,000,000, for example, 2,000 to 500,000, particularly 3,000 to 200,000. The number average molecular weight (Mn) of the water- and oil-repellent polymer is generally measured by GPC (gel permeation chromatography).

[0099] (B) Silicone polymer The silicone polymer has the formula: (R 53 ) 3 Si-O-[-Si(R 51 ) 2 -O-] a -[-Si(R 51 )(R 52 )-O-] b -Si(R 53 ) 3 [In the formula, R 51 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; R 52 each independently represents a saturated hydrocarbon group having 23 to 40 carbon atoms; R 53 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a saturated hydrocarbon group having 23 to 40 carbon atoms; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 5 to 200. It is a polymer represented by the formula:

[0100] R 51 and R 53 In the above, the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms may be unsubstituted or substituted. R 51 and R 53 Specific examples of R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group; a cyclopentyl group, a cyclohexyl group, a cycloheptyl group; a phenyl group, a tolyl group, a naphthyl group, or a group in which some or all of the hydrogen atoms bonded to these groups have been substituted with a halogen atom, an amino group, a cyano group, or the like. 51 and R 53 is preferably a methyl group or an ethyl group. R 51 and R 53 may have an alkyl group having 3 to 22 carbon atoms or an unsaturated hydrocarbon group having 8 to 40 carbon atoms (for example, a hydrocarbon group having an aromatic ring), but it is preferable that it does not have these groups. R 51 and R 53 In the above, the alkoxy group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0101] R is easy to manufacture industrially and is readily available. 51 and R 53 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0102] The silicone polymer has at least one saturated hydrocarbon group having 23 to 40 carbon atoms. The saturated hydrocarbon group having 23 to 40 carbon atoms may be linear or branched, and is preferably an alkyl group. Specific examples of the saturated hydrocarbon group having 23 to 40 carbon atoms include a tricosyl group (23 carbon atoms), a lignoceryl group (tetracosyl group, 24 carbon atoms), a cellotyl group (hexacosyl group, 26 carbon atoms), a monthyl group (octacosyl group, 28 carbon atoms), a melissyl group (triacontane group, 30 carbon atoms), and a dotriacontane group (32 carbon atoms).

[0103] a is an integer of equal to or greater than 0. In terms of ease of industrial production and availability, a is preferably equal to or less than 40, and more preferably equal to or less than 30.

[0104] The sum of a and b is 5 to 200. From the viewpoints of ease of industrial production, availability, and handling, the sum of a and b is preferably 10 to 100, and more preferably 40 to 60. a may be 0 to 150, for example, 1 to 100. The lower limit of b may be 1, 2, or 3, and the upper limit of b may be 150, 10, or 5.

[0105] When a or b is 2 or more, R exists multiple times. 51 and R 52 Each of may be the same or different. R 51 and R 52 Groups and R 53 It is preferred that at least 50 mol % of the total groups are methyl groups. The order of the repeating units bounded by a or b is not limited to the order shown in the chemical formula, but may be any order, i.e., the silicone polymer may be either a random polymer or a block polymer.

[0106] Examples of silicone polymers are as follows: TIFF2025022991000023.tif2371 [wherein a represents an integer of 0 to 150; b represents an integer from 1 to 150; (a+b) is 5 to 200; n is an integer from 19 to 36.

[0107] The amount of the silicone polymer may be 0.1 to 100 parts by weight, for example, 1 to 30 parts by weight, and particularly 2 to 10 parts by weight, based on 100 parts by weight of the water- and oil-repellent polymer.

[0108] The silicone polymer can be synthesized by a conventional method, for example, by subjecting a silicone having a SiH group to a hydrosilylation reaction with an α-olefin.

[0109] Examples of silicones having a SiH group include methylhydrogensilicone polymers having a degree of polymerization of 10 to 200, and copolymers of dimethylsiloxane and methylhydrogensiloxane. Among these, methylhydrogensilicone is preferred because it is easy to produce industrially and is readily available.

[0110] The α-olefin is a compound from which a saturated hydrocarbon group having a carbon number of 23 to 40 is derived in a silicone polymer. Specific examples of the α-olefin are 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triacontene, and 1-dotriacontene. The hydrosilylation reaction may be carried out by reacting the above-mentioned silicone having a SiH group with an α-olefin in a stepwise manner or all at once, if necessary in the presence of a catalyst.

[0111] The amounts of the SiH group-containing silicone and the α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent weight or number average molecular weight of the SiH group-containing silicone, respectively.

[0112] Examples of catalysts used in the hydrosilylation reaction include platinum and palladium compounds, and among these, platinum compounds are preferred, such as platinum(IV) chloride.

[0113] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be appropriately adjusted. The reaction temperature is, for example, 10 to 200° C., and preferably 50 to 150° C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150° C. The hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of the inert gas include nitrogen and argon. The reaction proceeds without a solvent, but a solvent may be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0114] (C) Liquid medium The water repellent composition contains a liquid medium, which may be an organic solvent, water, an organic solvent, or a mixture of water and an organic solvent. The water repellent composition is generally a solution or a dispersion. A solution is a solution in which a polymer is dissolved in an organic solvent. A dispersion is an aqueous dispersion in which a polymer is dispersed in an aqueous medium (water or a mixture of water and an organic solvent).

[0115] Examples of the organic solvent include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha, kerosene). The liquid medium may be water alone or a mixture of water and a (water-miscible) organic solvent. The amount of the organic solvent may be 30% by weight or less, for example 10% by weight or less (preferably 0.1% by weight or more) based on the liquid medium. It is preferable that the liquid medium is water alone.

[0116] (D) Surfactant When the water repellent composition is an aqueous dispersion, it preferably contains a surfactant. In the water repellent composition, the surfactant includes a nonionic surfactant. Furthermore, the surfactant preferably includes one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant.

[0117] (D1) Nonionic surfactant Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides. An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0118] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a monohydric to hexahydric (particularly dihydric to pentahydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a monohydric to hexahydric (particularly dihydric to pentahydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0119] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamine. An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups. The polyhydric alcohol may be a dihydric to pentahydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (eg, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0120] The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably 2 to 100. The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.

[0121] The nonionic surfactant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Moreover, the nonionic surfactant preferably has a structure that does not contain an aromatic group in view of environmental issues (biodegradability, environmental hormones, etc.).

[0122] The nonionic surfactant has the formula: R 1 O-(CH 2 CH 2 O) p -(R 2 O) q -R 3 [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or acyl group having 2 to 22 carbon atoms, R 2 each is independently the same or different and is an alkylene group having 3 or more carbon atoms (e.g., 3 to 10), R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number equal to or greater than 2, q is a number equal to or greater than 0.] The compound may be represented by the formula:

[0123] R 1 R preferably has 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms. 1 Preferred specific examples include a lauryl group, a tridecyl group, and an oleyl group. R 2 Examples are a propylene group and a butylene group. In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q may form a polyoxyalkylene chain. The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, and among these, an oxypropylene chain is preferred.

[0124] Specific examples of nonionic surfactants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C 12 -C 16 ) thiol, sorbitan mono fatty acid (C 7 -C 19 ) or alkyl (C 12 -C 18 ) amines and the like.

[0125] The proportion of the polyoxyethylene block may be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer). The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic surfactant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. An example of a compound having an HLB of less than 15 is a sorbitan fatty acid ester. An example of a compound having an HLB of 15 or more is a polyoxyethylene alkyl ether. The weight ratio of the compound having an HLB of less than 15 to the compound having an HLB of 15 or more may be 90:10 to 20:80, for example 85:15 to 55:45. The nonionic surfactant may be used alone or in combination of two or more kinds.

[0126] (D2) Cationic surfactant The cationic surfactant is preferably a compound having no amide group.

[0127] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene adduct ammonium salt.Specific examples of the cationic surfactant include, but are not limited to, amine salt surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc., alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, pyridinium salts, alkyl isoquinolinium salts, and quaternary ammonium salt surfactants such as benzethonium chloride.

[0128] Preferred examples of the cationic surfactant are: R 21 -N + (-R 22 )(-R 23 )(-R 24 ) X - [In the formula, R 21 , R 22 , R 23 and R 24 is a hydrocarbon group having 1 to 40 carbon atoms, X is an anionic group. It is a compound of the formula: R 21 , R 22 , R 23 and -R 24 Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0129] The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula: R 1 p - N + R 2 q X - [In the formula, R 1 is C12 or higher (e.g. C12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50); (CH 3 , C 2 H 5 is particularly preferred), X is a halogen atom (e.g., ), C 1 ~C 4 of fatty acid bases, p is 1 or 2, q is 2 or 3, and p+q=4. R 1 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0130] Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0131] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amido betaines, and betaine acetate. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetate betaine, and fatty acid amidopropyl dimethylamino acetate betaine.

[0132] The nonionic surfactant, cationic surfactant and amphoteric surfactant may each be used alone or in combination of two or more thereof. The amount of the cationic surfactant may be 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more, based on the total amount of the surfactants. The weight ratio of the nonionic surfactant to the cationic surfactant is preferably 95:5 to 20:80, more preferably 85:15 to 40:60. The amount of the cationic surfactant may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight, relative to 100 parts by weight of the polymer. The total amount of the surfactants may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight, relative to 100 parts by weight of the polymer.

[0133] (E) Other ingredients The surface treatment agent may contain at least one of a non-fluorine-containing water-repellent compound and an additive as components other than the water- and oil-repellent polymer, the liquid medium and the surfactant. (E1) Non-fluorinated water-repellent compound The surface treatment agent may contain a water-repellent compound that does not contain fluorine atoms (non-fluorine water-repellent compound). The non-fluorinated water repellent compound may be a non-fluorinated acrylate polymer, a saturated or unsaturated hydrocarbon compound, or a silicone-based compound.

[0134] The non-fluorinated acrylate polymer is a homopolymer constituted by one kind of non-fluorinated acrylate monomer, or a copolymer constituted by at least two kinds of non-fluorinated acrylate monomers, or a copolymer constituted by at least one kind of non-fluorinated acrylate monomer and at least one other kind of non-fluorinated monomer (an ethylenically unsaturated compound, for example, ethylene, a vinyl-based monomer). The non-fluorinated acrylate monomer constituting the non-fluorinated acrylate polymer is represented by the formula: CH 2 =CA-T [In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom, or an iodine atom), T is a hydrogen atom, a linear or cyclic hydrocarbon group having 1 to 40 carbon atoms, or a linear or cyclic organic group having 1 to 41 carbon atoms and an ester bond.] It is a compound represented by the formula:

[0135] Examples of the linear or cyclic hydrocarbon group having 1 to 40 carbon atoms include linear or branched aliphatic hydrocarbon groups having 1 to 40 carbon atoms, cyclic aliphatic groups having 4 to 40 carbon atoms, aromatic hydrocarbon groups having 6 to 40 carbon atoms, and aromatic aliphatic hydrocarbon groups having 7 to 40 carbon atoms.

[0136] Examples of the linear or cyclic organic group having 1 to 41 carbon atoms and an ester bond include -C(=O)-OQ and -OC(=O)-Q (wherein Q is a linear or branched aliphatic hydrocarbon group having 1 to 40 carbon atoms, a cyclic aliphatic group having 4 to 40 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 40 carbon atoms).

[0137] Examples of the non-fluorine-containing acrylate monomer include, for example, alkyl (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, and methoxypolypropylene glycol (meth)acrylate.

[0138] The non-fluorinated acrylate monomer is preferably an alkyl (meth)acrylate ester. The number of carbon atoms in the alkyl group may be 1 to 40, for example, 6 to 40 (e.g., 10 to 30). Specific examples of the non-fluorinated acrylate monomer are lauryl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate. The non-fluorinated acrylate polymer can be produced by the same polymerization method as that for the water- and oil-repellent polymer.

[0139] The saturated or unsaturated hydrocarbon compound is preferably a saturated hydrocarbon. In the saturated or unsaturated hydrocarbon compound, the carbon number may be 15 or more, preferably 20 to 300, for example, 25 to 100. A specific example of the saturated or unsaturated hydrocarbon compound is paraffin. Silicone compounds are generally used as water repellents. There are no limitations on the silicone compounds as long as they are water repellent. The amount of the non-fluorinated water-repellent compound may be 500 parts by weight or less, for example, 5 to 200 parts by weight, particularly 5 to 100 parts by weight, based on 100 parts by weight of the water- and oil-repellent polymer.

[0140] (E2) Additives The surface treatment agent may contain additives. Examples of additives include silicon-containing compounds, waxes, acrylic emulsions, etc. Other examples of additives include other fluorine-containing polymers, drying speed regulators, crosslinking agents, film-forming assistants, compatibilizers, surfactants, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, defoamers, texture modifiers, slippage modifiers, antistatic agents, hydrophilizing agents, antibacterial agents, preservatives, insect repellents, fragrances, flame retardants, etc.

[0141] The water- and oil-repellent polymer of the present disclosure can be produced by any of the usual polymerization methods, and the polymerization reaction conditions can be selected arbitrarily. Such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

[0142] In solution polymerization, a method is adopted in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, based on 100 parts by weight of the monomer.

[0143] The organic solvent is inert to the monomers and dissolves them, and may be, for example, an ester (e.g., an ester having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total of the monomers.

[0144] In emulsion polymerization, a method is adopted in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, the monomer is polymerized by stirring at a temperature in the range of 50 to 80°C for 1 to 10 hours. As the polymerization initiator, water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine-dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, and oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight per 100 parts by weight of the monomer.

[0145] In order to obtain a polymer aqueous dispersion having excellent shelf stability, it is desirable to polymerize the monomer by forming fine particles in water using an emulsifier capable of applying strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. In addition, various emulsifiers such as anionic, cationic or nonionic emulsifiers can be used as the emulsifier, and are used in the range of 0.5 to 20 parts by weight per 100 parts by weight of the monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible, it is preferable to add a compatibilizer that can sufficiently make these monomers compatible, such as a water-soluble organic solvent or a low molecular weight monomer. The addition of a compatibilizer can improve emulsifiability and copolymerizability.

[0146] Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol, which may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of water. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate, which may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of the total amount of the monomers.

[0147] In the polymerization, a chain transfer agent may be used. The molecular weight of the polymer can be changed depending on the amount of the chain transfer agent used. Examples of the chain transfer agent include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of the chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers.

[0148] The treatment agent of the present disclosure may be in the form of a solution, emulsion (particularly, an aqueous dispersion) or aerosol, but is preferably an aqueous dispersion. The treatment agent comprises a water- and oil-repellent polymer (the active component of the surface treatment agent) and a medium (particularly, a liquid medium, such as an organic solvent and / or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the treatment agent. In the treatment agent, the concentration of the water- and oil-repellent polymer may be 0.01 to 95% by weight, 0.1 to 60% by weight, for example, 5 to 50% by weight.

[0149] The treatment agent of the present disclosure can be applied to the object to be treated by a conventionally known method. Usually, the treatment agent is dispersed and diluted in an organic solvent or water, and then attached to the surface of the object to be treated by a known method such as dip coating, spray coating, foam coating, etc., and then dried. If necessary, the treatment agent may be applied together with a suitable crosslinking agent (e.g., blocked isocyanate) and cured. Furthermore, the treatment agent of the present disclosure may be used in combination with an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, etc. The concentration of the water- and oil-repellent polymer in the treatment liquid to be contacted with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example, 0.05 to 10% by weight.

[0150] Examples of objects to be treated with the treatment agent (e.g., water- and oil-repellent agent) of the present disclosure include textile products, stone materials, filters (e.g., electrostatic filters), dust masks, fuel cell parts (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Examples of textile products include various types of natural fibers from animals and plants, such as cotton, hemp, wool, and silk; synthetic fibers, such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers, such as rayon and acetate; inorganic fibers, such as glass fibers, carbon fibers, and asbestos fibers, and mixtures of these fibers.

[0151] The textile product may be in the form of fiber, cloth, or the like. The treatment of the present disclosure can be used as an internal or external mold release agent.

[0152] The water- and oil-repellent polymer can be applied to a fibrous substrate (e.g., a textile product) by any of the methods known for treating textile products with a liquid. When the textile product is a fabric, the fabric may be immersed in the solution, or the solution may be applied or sprayed onto the fabric. The treated textile product is dried and preferably heated, for example, at 100°C to 200°C, to develop oil repellency.

[0153] Alternatively, the water and oil repellent polymer may be applied to the textile by a cleaning method, such as in a laundry application or a dry cleaning method.

[0154] The treated textiles are typically fabrics, including woven, knitted and nonwoven fabrics, clothing forms of fabrics and carpets, but may also be fibers or yarns or intermediate textile products (such as slivers or rovings). The textile material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or leocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or may be a mixture of fibers (such as a mixture of natural and synthetic fibers). The water- and oil-repellent polymers of the present disclosure are particularly effective in rendering cellulosic fibers (such as cotton or rayon) oleophobic and oil-repellent. The method of the present disclosure also renders textiles hydrophobic and water-repellent in general.

[0155] Alternatively, the fibrous substrate may be leather. The water- and oil-repellent polymer may be applied to the leather from an aqueous solution or emulsion at various stages of the leather processing, for example during the wet processing of the leather or during the finishing of the leather, to render the leather hydrophobic and oil-repellent. Alternatively, the fibrous substrate may be paper. The repellent polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example during the drying period of the paper.

[0156] "Treatment" means that the treatment agent is applied to the object to be treated by immersion, spraying, coating, etc. Through the treatment, the polymer, which is the active ingredient of the treatment agent, penetrates into the inside of the object to be treated and / or adheres to the surface of the object to be treated. EXAMPLES

[0157] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples. In the following, parts or percentages or ratios refer to parts by weight or percentages by weight or ratios by weight, unless otherwise specified. The test procedure is as follows.

[0158] Water repellency test A treatment solution with a solid content of 1.5% was prepared, and the cloth was immersed in the test solution and passed through a mangle. The water repellency of the heat-treated test cloth was evaluated. The water repellency of the treated cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). It is expressed by a water repellency number as shown in the table below. The higher the score, the better the water repellency.

[0159] TIFF2025022991000024.tif49155

[0160] Strong water repellency test When testing using the spray method of JIS-L-1092 (AATCC-22), the ease with which water comes into contact with the fabric is repelled and the speed at which it flows off the fabric are visually evaluated. The results are expressed by a water repellency number as shown in the table below. The higher the score, the better the water repellency.

[0161] TIFF2025022991000025.tif65159

[0162] Washing durability test According to JIS L-0217 103, the test cloth was washed 10 times and then dried in a tumbler (60°C for 30 minutes) and the water repellency was evaluated.

[0163] Slip resistance test The slip resistance test was carried out according to JIS-L-1096 B method. Five 10cm x 17cm test pieces of polyester fabric (white) treated with a water repellent were taken in each of the vertical and horizontal directions, folded in half with the front side inside, cut along the fold, and sewn together 1cm from the cut end with a regular sewing machine needle of 11, using a lock stitch type, 5 stitches / cm, and polyester filament 78dex x 3 thread. Using a tensile tester, a specified load (49.0N (5kgf)) was applied using the grab method with a grip interval of 7.62cm and a tensile strength of 30cm per minute, after which the test piece was removed from the grip and left for 1 hour, and the size of the maximum hole in the slip at a load that would cause the slack around the stitching to disappear was visually observed. The test pieces with almost no holes were evaluated as "○", those with small holes as "△", and those with many holes as "×".

[0164] Water dispersion stability The aqueous dispersion was allowed to stand at room temperature, and the presence or absence of separation or solid matter was visually observed and evaluated according to the following criteria. ○: Uniform △: A small amount of separated solid matter is present ×: A lot of separated solids are present

[0165] Gum Up Rating 1000g of test liquid was prepared with water of hardness 16 so that the solids concentration of the aqueous dispersion was 1.8%, and placed in a pad that could be adjusted to a temperature of 40°C. A polyester cloth 20cm wide and 80cm long was looped around the mangle so that continuous treatment could be performed, and continuous treatment was performed for 1 hour at a mangle pressure of 0.4MPa. After 1 hour, the amount of solids adhering to the mangle was observed visually and by touch, and evaluated according to the following criteria. ○: No solid matter at all △: A little solid matter ×: Too much solid matter

[0166] Antifoaming evaluation A test liquid was prepared by mixing the polymer dispersion with water of hardness 43 so that the solid concentration was 0.3%, and the test liquid was heated to 40° C. Air was bubbled into the test liquid at 20 L / min for 10 minutes, and the foam height (unit: mm) was measured.

[0167] Texture evaluation Sensory evaluation was performed by five people on a five-point scale, and the average was calculated. 5: Very soft 4: Soft 3: Same as untreated fabric 2: Hard 1: Very hard

[0168] Chalk Mark Rating A plastic stick with a tip diameter of 5 mm was pressed against the treated fabric and traced, after which it was visually observed whether any trace remained on the fabric and rated on a 5-point scale as follows. 5: No trace at all 4: Almost no traces found 3: A few traces are visible 2: Traces are visible 1: Clear traces are visible

[0169] Synthesis Example 1 [Synthesis of C18URA (stearyl group-containing urethane acrylate)] TIFF2025022991000026.tif2152

[0170] A 1L four-neck flask was charged with 80.2g of hydroxyethyl acrylate, 100g of ethyl acetate, 0.03g of polymerization inhibitor, and 0.03g of tin catalyst. A stirring rod, thermometer, and reflux tube were set, and 201.4g of octadecyl isocyanate was dissolved in 100g of ethyl acetate and charged into the dropping funnel. The dropping funnel was set into the flask, and the temperature was raised to 70°C. The ethyl acetate solution of octadecyl isocyanate was gradually dripped from the dropping funnel over about 30 minutes, while taking care not to generate heat. After the dripping was completed, the reaction was allowed to proceed for another 2 hours. The reaction was terminated when it was confirmed by infrared spectroscopy (IR) that the isocyanate peak had disappeared. The reactant was reprecipitated in methanol, washed with methanol, and dried under reduced pressure to obtain a white powder. The reactant was 1 It was identified as C18URA by H-NMR. The melting point of the compound was about 73°C as determined by differential scanning calorimetry (DSC).

[0171] Synthesis Example 2 [Synthesis of C18ureaA (stearyl group-containing urea acrylate)] TIFF2025022991000027.tif2153

[0172] A 1L four-neck flask was charged with 200g of stearylamine, 100g of ethyl acetate, and 0.03g of polymerization inhibitor. A stirring rod, thermometer, and reflux tube were set, and 2-acryloyloxyethyl isocyanate was dissolved in 100g of ethyl acetate and charged into the dropping funnel. The dropping funnel was set into the flask, and the ethyl acetate solution of 2-acryloyloxyethyl isocyanate was gradually dropped from the dropping funnel at room temperature over about 30 minutes, while taking care not to generate heat. After the dropping was completed, the reaction was allowed to proceed for another 2 hours. The reaction was terminated when it was confirmed by infrared spectroscopy (IR) that the isocyanate peak had disappeared. The reactant was reprecipitated in methanol, washed with methanol, and dried under reduced pressure to obtain a white powder. The reactant was 1 H-NMR identified the compound as C18UreaA. Differential scanning calorimetry (DSC) showed that the compound had a melting point of approximately 83°C.

[0173] Synthesis Example 3 [Synthesis of C18ureaMA (stearyl group-containing urea methacrylate)] TIFF2025022991000028.tif3959(n=18)

[0174] A 1L four-neck flask was charged with 200g of stearylamine, 100g of ethyl acetate, and 0.03g of polymerization inhibitor. A stirring rod, thermometer, and reflux tube were set, and 2-methacryloyloxyethyl isocyanate was dissolved in 100g of ethyl acetate and charged into the dropping funnel. The dropping funnel was set into the flask, and the ethyl acetate solution of 2-methacryloyloxyethyl isocyanate was gradually dropped from the dropping funnel at room temperature over about 30 minutes, while taking care not to generate heat. After the dropping was completed, the reaction was allowed to proceed for another 2 hours. The reaction was terminated when it was confirmed by infrared spectroscopy (IR) that the isocyanate peak had disappeared. The reactant was reprecipitated in methanol, washed with methanol, and dried under reduced pressure to obtain a white powder. The reactant was 1 H-NMR identified the compound as C18ureaMA. Differential scanning calorimetry (DSC) showed that the compound had a melting point of approximately 91°C.

[0175] Manufacturing Example 1 A 200cc four-neck flask equipped with a nitrogen inlet tube, a thermometer, a stirring rod, and a reflux tube was charged with 40g of stearyl acrylate (StA), 0.04g of lauryl mercaptan (LSH), and 56g of toluene, and stirred at room temperature for 30 minutes under a nitrogen stream. Then, a solution of 0.4g of an azo group-containing oil-soluble polymerization initiator dissolved in 4g of toluene was added, and the temperature was raised to 80°C, and a polymerization reaction was carried out for 8 hours. After obtaining the polymer, more toluene was added to prepare a toluene solution 1 with a solid content concentration of 20%.

[0176] Manufacturing Examples 2 to 7 Polymerization was carried out in the same manner as in Production Example 1 using the compositions shown in Table 1 to obtain polymers, which were then diluted with toluene to prepare toluene solutions 2 to 7 each having a solid content of 20%.

[0177] Production Example 8 Add methyl hydrogen silicone oil ( 1SiH:SiCH measured by H NMR 3 The mixture was charged with 12 g of ethanol (molar ratio = 60:40) and 0.02 g of hydrosilylation Pt catalyst. A stirrer, thermometer, and reflux condenser were installed in the CH 2 =CH-(CH 2 CH 2 )n-CH 2 CH 3 (n=11) 36g was placed in a dropping funnel. CH 2 =CH-(CH 2 CH 2 )n-CH 2 CH 3 After the completion of the dropwise addition, the mixture was allowed to react for about 3 hours at 70° C. It was confirmed by infrared spectroscopy (IR) that the SiH peak had disappeared, and silicone polymer 6 was obtained.

[0178] Manufacturing Examples 9-10 Silicone polymers 9 to 10 were obtained by synthesis in the same manner as in Production Example 8 using the compositions shown in Table 2.

[0179] Comparative Manufacturing Examples 1-5 Comparative silicone polymers 1 to 5 were obtained by synthesizing the compositions shown in Table 2 in the same manner as in Production Example 8.

[0180] Manufacturing Example 11 In a 500ml plastic container, 30g of water-soluble glycol solvent, 40g of C6SFMA, 40g of stearyl acrylate (StA), 180g of pure water, 2g of cationic emulsifier, 2g of sorbitan fatty acid ester, and 6g of polyoxyethylene alkyl were charged, heated to 60°C, stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasonic waves for 15 minutes. The emulsified dispersion was transferred to a 500ml autoclave, and after nitrogen replacement, 0.2g of lauryl mercaptan (LSH) and 20g of vinyl chloride were charged. Furthermore, 1g of an azo group-containing water-soluble initiator was added, heated to 60°C, and reacted for 4 hours to obtain an aqueous dispersion of a polymer. This dispersion was further diluted with pure water to prepare aqueous dispersion 9 with a solid content concentration of 20%.

[0181] Manufacturing Examples 12 and 14 Polymerization was carried out in the same manner as in Production Example 11 using the composition shown in Table 3. After obtaining a polymer, it was further diluted with pure water to prepare aqueous dispersions 12 and 14 having a solid content concentration of 30%.

[0182] Manufacturing Examples 15-18, 20-22 After charging the compositions shown in Table 3, polymerization was carried out in the same manner as in Production Example 11 except for heating to 80°C. After obtaining the polymer, it was further diluted with pure water to prepare aqueous dispersions 15 to 18 and 20 to 22 with a solid content concentration of 30%.

[0183] Manufacturing Example 13 In a 500ml poly container, 17g of water-soluble glycol solvent, 60g of StA, 136g of pure water, 0.6g of cationic emulsifier, 1g of sorbitan fatty acid ester, and 4.4g of polyoxyethylene alkyl ether were charged, heated to 60°C, stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. The emulsified dispersion was transferred to a 500cc four-neck flask equipped with a nitrogen inlet tube, a thermometer, a stirring rod, and a reflux tube, and after nitrogen replacement, 0.1g of LSH was charged and stirred, and then 0.6g of an azo group-containing water-soluble initiator was added, heated to 60°C, and reacted for 4 hours to obtain an aqueous dispersion of a polymer. Then, pure water was added to prepare an aqueous dispersion 13 with a solids concentration of 30%.

[0184] Manufacturing Example 19 After the composition shown in Table 3 was charged, polymerization was carried out in the same manner as in Production Example 13 except for heating to 80°C. After the polymer was obtained, it was further diluted with pure water to prepare aqueous dispersion 19 having a solid content concentration of 30%.

[0185] Manufacturing Example 23 A 250ml plastic container was charged with 28g of silicone polymer 8, 5.6g of water-soluble glycol solvent, 60g of pure water, 1.7g of sorbitan fatty acid ester (HLB5 or less), 0.7g of polyoxyethylene alkyl ether (HLB15 or more), and 0.6g of cationic emulsifier, heated to 75°C, stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasonic waves for 10 minutes to obtain an aqueous dispersion. Pure water was then added to prepare an aqueous dispersion 23 with a solid content concentration of 30%.

[0186] Manufacturing Examples 24-25 Aqueous dispersions were obtained using the compositions shown in Table 4 in the same manner as in Production Example 23, and then further diluted with pure water to prepare aqueous dispersions 24 to 25 with solid concentrations of 30%.

[0187] Comparative Example 6 A 250ml plastic container was charged with 28g of comparative silicone polymer 1, 5.6g of water-soluble glycol solvent, 60g of pure water, 1.7g of sorbitan fatty acid ester (HLB5 or less), 0.7g of polyoxyethylene alkyl ether (HLB15 or more), and 0.6g of cationic emulsifier, heated to 75°C, stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 10 minutes to obtain an aqueous dispersion. Pure water was then added to prepare comparative aqueous dispersion 6 with a solids concentration of 30%.

[0188] Comparative Manufacturing Examples 7-13 Aqueous dispersions were obtained using the compositions shown in Table 4 in the same manner as in Comparative Production Example 6, and then further diluted with pure water to prepare Comparative Aqueous Dispersions 7 to 13 with solid concentrations of 30%.

[0189] The abbreviations have the following meanings: TIFF2025022991000029.tif75155

[0190] [Table 1]

[0191] [Table 2]

[0192] [Table 3]

[0193] [Table 4]

[0194] Test Example 1 Toluene solution 1 with a solid content concentration of 20% prepared in Production Example 1 and silicone polymer 8 prepared in Production Example 8 were prepared so that the solid content weight ratio was 3:1, and further diluted with toluene to prepare a treatment solution with a solid content concentration of 1.5%. Polyester cloth (gray), nylon cloth (black), and cotton cloth (beige) were immersed in this treatment solution, and then lightly subjected to a centrifugal spin-drying machine for about 10 seconds. The wet pickup was about 65% (polyester cloth), about 40% (nylon cloth), and about 95% (cotton cloth). After drying the treated cloth overnight at room temperature, it was passed through a pin tenter at 170°C for 3 minutes and cured. The test cloth thus treated was evaluated for water repellency by the water repellency test by the spray method and the strong water repellency test according to JIS L-1092. The water repellency results are shown in Table 5.

[0195] Test Examples 2 to 7 Each of the toluene solutions 2 to 7 with a solid content concentration of 20% prepared in Production Examples 2 to 7 and the silicone polymer 8 prepared in Production Example 8 were diluted with toluene (solid content concentration 1.5%) in the same manner as in Test Example 1, and a water repellency test was performed by treating fabric in the same manner as in Test Example 1. The results are shown in Table 5.

[0196] Test Examples 8-9 Each of the toluene solutions 7 with a solid content of 20% prepared in Production Example 7 and the silicone polymers 9 to 10 prepared in Production Examples 9 to 10 were diluted with toluene (solid content concentration 1.5%) in the same manner as in Test Example 1, and a water repellency test was performed by treating fabric in the same manner as in Test Example 1. The results are shown in Table 5.

[0197] Comparative test example 1 The toluene solution 1 having a solid content concentration of 20% prepared in Production Example 1 was further diluted with toluene to a solid content concentration of 1.5%, and a water repellency test was performed by treating a cloth in the same manner as in Test Example 1. The results are shown in Table 5.

[0198] Comparative test examples 2-7 Each of the toluene solutions 2 to 7 having a solid content of 20% prepared in Production Examples 2 to 7 was diluted with toluene (solid content concentration: 1.5%) in the same manner as in Comparative Test Example 1, and a water repellency test was performed by treating a cloth in the same manner as in Test Example 1. The results are shown in Table 5.

[0199] Comparative Test Example 8 Silicone polymer 8 prepared in Production Example 8 was diluted with toluene (solids concentration 1.5%) and a water repellency test was carried out by treating fabric in the same manner as in Test Example 1. The results are shown in Table 5.

[0200] Comparative Test Example 9 Each toluene solution 1 with a solids concentration of 20% prepared in Production Example 1 and the comparative silicone polymer 1 prepared in Comparative Production Example 1 were diluted with toluene (solids concentration 1.5%) in the same manner as in Test Example 1, and a water repellency test was performed by treating fabric in the same manner as in Test Example 1. The results are shown in Table 5.

[0201] Comparative Test Example 10 Each toluene solution 7 with a solids concentration of 20% prepared in Production Example 7 and the comparative silicone polymer 1 prepared in Comparative Production Example 1 were diluted with toluene (solids concentration 1.5%) in the same manner as in Test Example 1, and a water repellency test was performed by treating cloth in the same manner as in Test Example 1. The results are shown in Table 5.

[0202] Test Example 10 Aqueous dispersion 11 with a solid content of 30% prepared in Production Example 11 and aqueous dispersion 23 with a solid content of 30% prepared in Production Example 23 were prepared in a weight ratio of 90:10, and further diluted with tap water to prepare a treatment liquid with a solid content of 1.5%. Polyester cloth (gray), nylon cloth (black), and polyester cloth (white) were immersed in this treatment liquid and then squeezed with a mangle. The wet pickup was about 55% (polyester cloth black), about 35% (nylon cloth), and about 65% (polyester cloth white). This treated cloth was passed through a pin tenter at 170°C for 1 minute, dried, and cured. The test cloth thus treated was evaluated for water repellency by the water repellency test using the spray method and the strong water repellency test according to JIS L-1092. The water repellency results are shown in Table 6. Furthermore, in accordance with JIS L-0217 103, the test cloth was washed 10 times and then dried in a tumbler (at 60° C. for 30 minutes), and the results of the evaluation of water repellency are also shown in Table 6. The polyester fabric (white) was subjected to a slip resistance test in accordance with JIS-L-1096 B method, and the polyester fabric (gray) was subjected to a texture evaluation and a chalk mark evaluation. The results are shown in Table 7.

[0203] Test Examples 11-18, 24-26 Aqueous dispersions 12 to 22 with a solid content of 30% prepared in Production Examples 12 to 22 and aqueous dispersion 23 with a solid content of 30% prepared in Production Example 23 were prepared in a weight ratio of 90:10, and a treatment liquid was prepared in the same manner as in Test Example 10. This treatment liquid was used to treat cloth in the same manner as in Test Example 6, and a water repellency test was performed. The results are shown in Table 6.

[0204] Test Examples 19-20 A treatment liquid was prepared in the same manner as in Test Example 6, except that the weight ratios of aqueous dispersion 14 having a solid content of 30% prepared in Production Example 14 and aqueous dispersion 23 having a solid content of 30% prepared in Production Example 23 were adjusted to 95:5 and 80:20, respectively. A water repellency test was carried out by treating a cloth with this treatment liquid in the same manner as in Test Example 6. The results are shown in Table 6.

[0205] Test Examples 21-22 A treatment liquid was prepared in the same manner as in Test Example 10, except that aqueous dispersion 14 having a solid content concentration of 30% prepared in Production Example 14 and aqueous dispersions 24 and 25 having a solid content concentration of 30% prepared in Production Examples 24 and 25 were used. A water repellency test was performed by treating a cloth with this treatment liquid in the same manner as in Test Example 10. The results are shown in Table 6.

[0206] Test Example 23 Aqueous dispersion 18 having a solid content of 30% prepared in Production Example 18 and aqueous dispersion 24 having a solid content of 30% prepared in Production Example 24 were prepared in a weight ratio of 90:10, and a treatment liquid was prepared in the same manner as in Test Example 10. This treatment liquid was used to treat cloth in the same manner as in Test Example 10, and a water repellency test was performed. The results are shown in Table 6.

[0207] Test Example 27 Aqueous dispersion 13 with a solid content of 30% prepared in Production Example 13 and aqueous dispersion 23 with a solid content of 30% prepared in Production Example 23 were prepared in a weight ratio of 90:10, and MDI-based blocked isocyanate (solid content concentration 20%) was added to the aqueous dispersion to a solid content concentration of 0.1%, and the aqueous dispersion was diluted with tap water to prepare a treatment liquid in the same manner as in Test Example 10. This treatment liquid was used to treat cloth in the same manner as in Test Example 10, and a water repellency test was performed. The results are shown in Table 6.

[0208] Test Example 28 Aqueous dispersion 22 with a solid content of 30% prepared in Production Example 22 and aqueous dispersion 23 with a solid content of 30% prepared in Production Example 23 were prepared in a weight ratio of 90:10, and MDI-based blocked isocyanate (solid content concentration 20%) was added to the aqueous dispersion to a solid content of 0.1%, and the aqueous dispersion was diluted with tap water to prepare a treatment liquid in the same manner as in Test Example 10. This treatment liquid was used to treat cloth in the same manner as in Test Example 10, and a water repellency test was performed. The results are shown in Table 6.

[0209] Comparative Test Example 11 Aqueous dispersion 11 with a solid content of 30% prepared in Production Example 11 and comparative aqueous dispersion 7 with a solid content of 30% prepared in Comparative Production Example 7 were prepared in a weight ratio of 90:10, and diluted with tap water to a solid content of 1.5% to prepare a treatment liquid. This treatment liquid was used to treat fabric in the same manner as in Test Example 10, and a water repellency test was performed. The results are shown in Table 6.

[0210] Comparative Test Examples 12-19, 25-27 Aqueous dispersions 12 to 22 with a solid content of 30% prepared in Production Examples 12 to 22 and comparative aqueous dispersion 7 with a solid content of 30% prepared in Comparative Production Example 7 were prepared as in Comparative Test Example 7. This treatment liquid was used to treat cloth in the same manner as in Test Example 10, and a water repellency test was carried out. The results are shown in Table 6.

[0211] Comparative test examples 20, 28-30 A treatment liquid was prepared by diluting the aqueous dispersions 14, 21 to 23 prepared in Production Examples 14, 21 to 23 at a solid content concentration of 30% with tap water to a solid content concentration of 1.5%. A water repellency test was carried out by treating a cloth with this treatment liquid in the same manner as in Test Example 10. The results are shown in Table 6.

[0212] Comparative test examples 21-24 A treatment liquid was prepared in the same manner as in Comparative Test Example 11 using aqueous dispersion 14 with a solid content of 30% prepared in Production Example 14 and comparative aqueous dispersions 6, 8 to 10 with a solid content of 30% prepared in Comparative Production Examples 6, 8 to 10. A water repellency test was carried out by treating cloth with this treatment liquid in the same manner as in Test Example 6. The results are shown in Table 6.

[0213] Comparative Test Example 31 Aqueous dispersion 11 with a solid content concentration of 30% prepared in Production Example 11 was diluted with tap water to prepare a treatment solution with a solid content concentration of 1.5%. A polyester cloth (gray) was immersed in this treatment solution and then squeezed with a mangle. The wet pickup was about 55%. This treated cloth was passed through a pin tenter at 170°C for 1 minute, dried and cured. Using the test cloth thus treated, texture evaluation and chalk mark evaluation were performed. The results are shown in Table 8.

[0214] Comparative Test Example 32 The aqueous dispersion 12 with a solid content concentration of 30% prepared in Production Example 12 was diluted with tap water to prepare a treatment solution with a solid content concentration of 1.5%. A polyester cloth (gray) was immersed in this treatment solution and then squeezed with a mangle. The wet pickup was about 55%. The treated cloth was passed through a pin tenter at 170°C for 1 minute, dried and cured. The test cloth thus treated was used to perform a texture evaluation and a chalk mark evaluation. The results are shown in Table 8.

[0215] A slippage resistance test was carried out for Test Examples 13, 21, and 22 and Comparative Test Examples 14, and 20 to 24. The results are shown in Table 7. For Test Examples 10-11, 13, 20-21, 24-25, 29-30 and Comparative Test Examples 16, 28-29, 31-32, in addition to the texture evaluation and chalk mark evaluation, the gum-up evaluation and defoaming evaluation of the treatment liquid were also performed. The results are shown in Table 8.

[0216] [Table 5-1]

[0217] [Table 5-2]

[0218] [Table 6-1]

[0219] [Table 6-2]

[0220] [Table 6-3]

[0221] [Table 6-4]

[0222] [Table 7]

[0223] [Table 8] [Industrial Applicability]

[0224] The surface treatment agent of the present disclosure can be used, for example, as a water / oil repellent, an antifouling agent, and a soil release agent.

Claims

1. (A) 30 to 100% by weight of the water- and oil-repellent polymer is a repeating unit derived from at least one water- and oil-repellent monomer selected from the group consisting of a fluorine-containing monomer (A1) and a non-fluorine-containing monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms. A water- and oil-repellent polymer having the formula: (B) Formula: (R 53 ) 3 Si-O-[-Si(R 51 ) 2 -O-] a -[-Si(R 51 )(R 52 )-O-] ｂ -Si(R 53 ) 3 [In the formula, R ５１ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; R ５２ each independently represents a saturated hydrocarbon group having 23 to 40 carbon atoms; R ５３ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a saturated hydrocarbon group having 23 to 40 carbon atoms; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 10 to 200. and a silicone polymer represented by the formula: (C) Liquid medium A surface treatment agent comprising:

2. the water- and oil-repellent monomer is a fluorine-containing monomer (A1); The fluorine-containing monomer (A1) has the formula: CH ２ =C(-X １１ )-C(=O)-Y １１ -Z １１ -Rf [In the formula, X １１ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y １１ is —O— or —NH—, Z １１ is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms.

2. The surface treatment agent according to claim 1, which is a compound represented by the following formula:

3. In the fluorine-containing monomer (A1), X １１ is a hydrogen atom, a methyl group or a chlorine atom, and Y １１ is -O-, and Z １１ 3. The surface treatment agent according to claim 2, wherein Rf is a direct bond or an alkylene group having 1 to 20 carbon atoms, and Rf is a perfluoroalkyl group.

4. The surface treatment agent according to claim 2, wherein in the fluorine-containing monomer (A1), Rf has 1 to 6 carbon atoms.

5. 2. The surface treatment agent according to claim 1, wherein the water- and oil-repellent monomer is a non-fluorine-containing monomer (A2).

6. The fluorine-free monomer (A2) is represented by the formula: CH 2 =C(-X)-C(=O)-Y-R ｎ [In the formula, X is a hydrogen atom, a monovalent organic group, or a halogen atom, Y is a divalent to tetravalent linking group having at least one group selected from -O- and -NH-; R is a hydrocarbon group having 7 to 40 carbon atoms; n is an integer from 1 to 3.

6. The surface treatment agent according to claim 5, which is a monomer represented by the following formula:

7. In the non-fluorine monomer (A2), Y is -Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R' -Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, Y′ is a direct bond, —O—, or —NH—; R' is -(CH ２ ) m -(m is an integer from 1 to 5) or -C ６ H ６ -(phenylene group). The surface treatment agent according to claim 6,

8. The fluorine-free monomer (A2) is represented by the formula: CH 2 =C(-X １ )-C(=O)-Y １ -R １ [In the formula, X １ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y １ is —O— or —NH—, R １ is a hydrocarbon group having 7 to 40 carbon atoms. A compound represented by the formula: CH 2 =C(-X ２ )-C(=O)-Y ２ -Z １ (-Z ２ -R ２ ) ｐ [In the formula, X ２ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y ２ is —O— or —NH—, Z １ is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, Z ２ each independently represents a divalent to tetravalent linking group having at least one group selected from a direct bond, —O—, and —NH—; R ２ are each independently a hydrocarbon group having 7 to 40 carbon atoms, p is 1 or 2. and compounds of the formula: R ２２ -C(=O)-NH-R ２３ -O-R ２１ [In the formula, R ２１ represents an organic residue having an ethylenically unsaturated polymerizable group, R ２２ represents a hydrocarbon group having 7 to 40 carbon atoms, R ２３ is a hydrocarbon group having 1 to 5 carbon atoms.

8. The surface treatment agent according to claim 1, which is at least one monomer selected from the group consisting of compounds represented by the following formula:

9. The fluorine-containing monomer (A1) is CH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -C 6 F 13 CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -C 6 F 13 and CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -C 6 F 13 At least one compound selected from the group consisting of The fluorine-free monomer (A2) is stearyl (meth)acrylate and behenyl (meth)acrylate, Palmitic acid amidoethyl acrylate and stearic acid amidoethyl acrylate, [In the above formula, m is an integer of 1 to 5, and n is an integer of 7 to 40.], and In the above chemical formula, a methacrylate having a methyl group at the α-position and an acrylate having a chlorine atom at the α-position, 2. The surface treatment agent according to claim 1, which is at least one compound selected from the group consisting of lauryl (meth)acrylamide, cetyl (meth)acrylamide, stearyl (meth)acrylamide and behenyl (meth)acrylamide.

10. the amount of the water- and oil-repellent polymer (A) is 0.1 to 60% by weight based on the weight of the surface treatment agent; 10. The surface treatment agent according to claim 1, wherein the amount of the silicone polymer (B) is 1 to 100 parts by weight per 100 parts by weight of the water- and oil-repellent polymer (A).

11. The water- and oil-repellent polymer is (A3) a repeating unit derived from a non-fluorine-containing non-crosslinkable monomer, and (A4) Repeating unit derived from a non-fluorine crosslinkable monomer The surface treatment agent according to any one of claims 1 to 10, further comprising at least one selected from the group consisting of:

12. the fluorine-free non-crosslinkable monomer (A3) is at least one compound selected from the group consisting of vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, vinylidene bromide, and vinylidene iodide, The surface treatment agent according to claim 11, wherein the non-fluorine-containing crosslinkable monomer (A4) is at least one compound selected from the group consisting of diacetone acrylamide, (meth)acrylamide, N-methylol acrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, butadiene, isoprene, chloroprene and glycidyl (meth)acrylate.

13. In the silicone polymer, R ５１ and R ５３ The surface treatment agent according to any one of claims 1 to 9, wherein is not an alkyl group having 3 to 22 carbon atoms.

14. In the silicone polymer, R ５１ and R ５３ Each of the groups represented by the formula (1) is independently a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms.

15. the amount of the water- and oil-repellent monomer is 32 to 98% by weight based on the water- and oil-repellent polymer (A); the amount of the non-fluorine-containing non-crosslinkable monomer (A3) is 2 to 68% by weight based on the water- and oil-repellent polymer, 13. The surface treatment agent according to claim 11 or 12, wherein the amount of the non-fluorine-crosslinkable monomer (A4) is 50 parts by weight or less based on 100 parts by weight of the water / oil repellent monomer.

16. The surface treatment agent according to any one of claims 1 to 13, which is a water / oil repellent, an antifouling agent or a soil release agent.

17. (A) 30 to 100% by weight of the water- and oil-repellent polymer is a repeating unit derived from at least one water- and oil-repellent monomer selected from the group consisting of a fluorine-containing monomer (A1) and a non-fluorine-containing monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms. An auxiliary used in a surface treatment agent containing a water- and oil-repellent polymer having the formula: (B) Formula: (R 53 ) 3 Si-O-[-Si(R 51 ) 2 -O-] a -[-Si(R 51 )(R 52 )-O-] ｂ -Si(R 53 ) 3 [In the formula, R ５１ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; R ５２ each independently represents a saturated hydrocarbon group having 23 to 40 carbon atoms; R ５３ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a saturated hydrocarbon group having 23 to 40 carbon atoms; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 10 to 200. The auxiliary comprises a silicone polymer represented by the formula:

18. (B) Formula: (R 53 ) 3 Si-O-[-Si(R 51 ) 2 -O-] a -[-Si(R 51 )(R 52 )-O-] ｂ -Si(R 53 ) 3 [In the formula, R ５１ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; R ５２ each independently represents a saturated hydrocarbon group having 23 to 40 carbon atoms; R ５３ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a saturated hydrocarbon group having 23 to 40 carbon atoms; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 10 to 200. Use of a silicone polymer represented by the formula: The auxiliary comprises repeating units derived from at least one water- and oil-repellent monomer selected from the group consisting of a fluorine-containing monomer (A1) and a non-fluorine-containing monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms, in an amount of 30 to 100% by weight based on the water- and oil-repellent polymer (A). The use in a surface treatment agent comprising a water- and oil-repellent polymer having the formula:

19. (i) a step of polymerizing, in the presence of a liquid medium, a monomer containing at least one water- and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine-containing monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms to obtain an aqueous dispersion of a water- and oil-repellent polymer (A) having a repeating unit derived from the water- and oil-repellent monomer in an amount of 30 to 100% by weight based on the water- and oil-repellent polymer; (ii) adding a silicone polymer (B) to the aqueous dispersion of the water- and oil-repellent polymer A method for producing the surface treatment agent according to any one of claims 1 to 16, comprising the steps of:

20. A method for producing a treated substrate, comprising applying the surface treatment agent according to any one of claims 1 to 16 to a substrate.

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