Surface treatment agent

Abstract

To provide a surface treatment agent that imparts excellent water and oil repellency, particularly water repellency, to a substrate such as a fiber. (A) a water- and oil-repellent polymer having repeating units derived from at least one water- and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine-containing monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms; Formula (B): R 53 3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )(R 52 )-O-] b -SiR 53 3 [In the formula, R 51 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 is a saturated hydrocarbon group having 23 to 40 carbon atoms, R 53 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 is an integer of 0 or greater, b is an integer of 1 or greater, and (a+b) is 10 to 200. a silicone polymer represented by the formula: (C) Liquid medium A surface treatment agent comprising:

Description

[Technical Field]

[0001] This disclosure relates to surface treatment agents comprising water- and oil-repellent polymers and silicone polymers. Specifically, the surface treatment agents of this disclosure can impart excellent water-repellent, oil-repellent, and stain-resistant properties to textile products (e.g., carpets), paper, nonwoven fabrics, stone materials, electrostatic filters, dust masks, and fuel cell components. [Background technology]

[0002] Conventionally, fluorine-containing water- and oil-repellent agents containing fluorine compounds are known. When these water- and oil-repellent agents are applied to substrates such as textile products, they exhibit good water- and oil-repellent properties. Recent research findings, 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 revealed concerns about the environmental impact of PFOA (perfluorooctanoic acid), a type of long-chain fluoroalkyl compound. On April 14, 2003, the EPA (U.S. Environmental Protection Agency) announced that it would strengthen its scientific investigation into 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) have published that telomers may produce PFOA through degradation or metabolism (telomers refer to long-chain fluoroalkyl groups). Furthermore, it has been revealed that telomer is used in many products, including foam fire extinguishing agents, care products, cleaning products, carpets, textiles, paper, and leather, which are given water-repellent, oil-repellent, and stain-resistant properties. There are concerns that fluorine-containing compounds may accumulate in the environment.

[0003] Patent Document 1 (Japanese Unexamined Patent Publication No. 2017-155095) discloses a non-fluorinated water-repellent composition comprising a water-repellent additive and a non-fluorinated water-repellent agent. The organo-modified silicone, which is the water-repellent additive, has a hydrocarbon group having 8 to 40 carbon atoms or an alkyl group having 3 to 22 carbon atoms that has an aromatic ring.

[0004] Patent document 2 (International Publication No. 2016 / 048684) discloses a method for imparting water-repellent and oil-repellent properties using a non-fluorine urethane polymer. Patent document 3 (International Publication No. 2016 / 048642) discloses a method of imparting water repellency using a polymer formed from a non-fluorine monomer derived from a sugar alcohol. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2017-155095 [Patent Document 2] International Publication No. 2016 / 048684 [Patent Document 3] International Publication No. 2016 / 048642 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] One objective of this disclosure is to provide a surface treatment agent (particularly a water repellent agent) that imparts excellent water-repellent and oil-repellent properties, especially water-repellent properties, to a substrate such as fibers. Another object of this disclosure is to provide a surface treatment agent that provides excellent slip resistance to a substrate such as fibers. [Means for solving the problem]

[0007] This disclosure is, (A) Repeating units derived from at least one water- and oil-repellent monomer selected from fluorine-containing monomers (A1) and non-fluorine monomers (A2) having hydrocarbon groups with 7 to 40 carbon atoms. A water-repellent and oil-repellent polymer having the following properties: (B) Silicone polymer, and (C) Liquid media The present invention provides a surface treatment agent comprising the above. Furthermore, this disclosure states that (A) Repeating units derived from at least one water- and oil-repellent monomer selected from fluorine-containing monomers (A1) and non-fluorine monomers (A2) having hydrocarbon groups with 7 to 40 carbon atoms. An auxiliary agent used in a surface treatment agent containing a water-repellent and oil-repellent polymer having the following properties: The above-mentioned silicone polymer is provided as an auxiliary agent. In addition, this disclosure states that (i) In the presence of a liquid medium, polymerizing a monomer containing at least one water- and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine monomer (A2) having a hydrocarbon group with 7 to 40 carbon atoms to obtain an aqueous dispersion of a water- and oil-repellent polymer (A), and (ii) a step of adding a silicone polymer (B) to the aqueous dispersion of the water- and oil-repellent polymer A method for producing a surface treatment agent is also provided. Furthermore, the present disclosure provides a method for producing a treated substrate, which includes applying the surface treatment agent to the substrate.

[0008] Preferred embodiments of the present disclosure are as follows. [1] (A) Repeating units derived from at least one water- and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine monomer (A2) having a hydrocarbon group with 7 to 40 carbon atoms, accounting for 30 to 100% by weight based on the water- and oil-repellent polymer A water- and oil-repellent polymer having (B) Formula: (R 53 )3Si - O - [-Si(R 51 )2 - O -] a -[-Si(R 51 )(R 52 ) - O -] b -Si(R 53 )3 [In the formula, each R 51 independently represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an alkoxy group with 1 to 4 carbon atoms, each R 52 independently represents a saturated hydrocarbon group with 23 to 40 carbon atoms, each R 53 independently represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, or a saturated hydrocarbon group with 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.] A silicone polymer represented by, and (C) Liquid media A surface treatment agent comprising the above.

[0009] [2] The water- and oil-repellent monomer is a fluorine-containing monomer (A1), The fluorine-containing monomer (A1) is given by formula: CH2=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 These are directly bonded or divalent organic groups, Rf is a fluoroalkyl group having 1 to 20 carbon atoms. A surface treatment agent as described in [1], which is a compound represented by [1].

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

[0011] [5] The surface treatment agent according to [1], wherein the water-repellent and oil-repellent monomer is a non-fluorine monomer (A2). [6] The nonfluorine monomer (A2) is given by formula: CH2=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 with 7 to 40 carbon atoms. n is an integer between 1 and 3. The surface treatment agent described in [5] is a monomer represented by [5].

[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 -(CH2) m -(m is an integer between 1 and 5) or -C6H6- (phenylene group). The surface treatment agent described in [6].

[0013] [8] The nonfluorine monomer (A2) is given by formula: CH2=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 This refers to a hydrocarbon group with 7 to 40 carbon atoms. The compound shown by, formula: CH2=C(-X 2 )-C(=O)-Y 2 -Z 1 ( newZ 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 1This is a directly bonded, divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms. Z 2 Each of these is a divalent to tetravalent linking group having at least one group selected from direct bonds, -O-, and -NH-, R 2 These are, independently, hydrocarbon groups having 7 to 40 carbon atoms. p is either 1 or 2. Compounds represented by, and formula: R 22 -C(=O)-NH-R 23 -OR 21 [In the formula, R 21 This is an organic residue having an ethylenically unsaturated polymerizable group. R 22 These are hydrocarbon groups with 7 to 40 carbon atoms. R 23 This is a hydrocarbon group having 1 to 5 carbon atoms. A surface treatment agent according to any one of [1] to [7], which is at least one monomer selected from the group consisting of compounds represented by [1].

[0014] [9] Fluorine-containing monomer (A1) CH2=C(-H)-C(=O)-O-(CH2)2-C6F 13 CH2=C(-CH3)-C(=O)-O-(CH2)2-C6F 13 and CH2=C(-Cl)-C(=O)-O-(CH2)2-C6F 13 It is at least one compound selected from the group consisting of the following: The nonfluorine monomer (A2) Stearyl (meth)acrylate and behenyl (meth)acrylate, Palmitic acid amidoethyl acrylate and stearic acid amidoethyl acrylate, TIFF0007845919000001.tif2044 TIFF0007845919000002.tif2152 TIFF0007845919000003.tif2253 TIFF0007845919000004.tif2153 TIFF0007845919000005.tif2357 TIFF0007845919000006.tif2357 TIFF0007845919000007.tif2361 TIFF0007845919000008.tif2563 TIFF0007845919000009.tif2363 TIFF0007845919000010.tif2966 TIFF0007845919000011.tif3069 [In the above formula, m is an integer from 1 to 5, and n is an integer from 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, and 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 relative to the surface treatment agent. A surface treatment agent according to any one of [1] to [9], wherein the amount of silicone polymer (B) is 1 to 100 parts by weight per 100 parts by weight of water-repellent and oil-repellent polymer (A).

[11] Water-repellent and oil-repellent polymers, (A3) Repeating units derived from nonfluorine-free, non-crosslinkable monomers, and (A4) Repeating units derived from nonfluorine crosslinkable monomers A surface treatment agent according to any one of the following [1] to

[10] , further comprising at least one selected from the group consisting of [1] to

[10] .

[0016]

[12] The nonfluorine, non-crosslinked 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 crosslinkable monomer (A4) is at least one compound selected from the group consisting of diacetone acrylamide, (meth)acrylamide, N-methylolacrylamide, 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-derived materials, R 51 and R 53 The surface treatment agent is one of the following [1] to

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

[14] In silicone-derived materials, R 51 and R 53 Each of the following is independently a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms: a surface treatment agent according to any of [1] to

[13] .

[0018]

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

[11] or

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

[0019]

[16] A surface treatment agent according to any one of the following [1] to

[13] , wherein the surface treatment agent is a water-repellent or oil-repellent agent, an antifouling agent, or a dirt-removing agent.

[17] (A) Repeating units derived from at least one water- and oil-repellent monomer selected from fluorine-containing monomers (A1) and non-fluorine monomers (A2) having hydrocarbon groups with 7 to 40 carbon atoms, in an amount of 30 to 100% by weight relative to the water- and oil-repellent polymer. An auxiliary agent used in a surface treatment agent containing a water-repellent and oil-repellent polymer having the following properties: Formula (B): (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )(R 52 )-O-] b -Si(R 53 )3 [In the formula, R 51 Each of these 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 of these independently represents a saturated hydrocarbon group with 23 to 40 carbon atoms. R 53 Each of these 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 greater than or equal to 0, b represents an integer greater than or equal to 1, and (a+b) is between 10 and 200. An additive consisting of a silicone polymer as shown.

[0020]

[18] Formula (B): (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )(R 52 )-O-] b -Si(R 53 )3 [In the formula, R 51 Each of these 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 of these independently represents a saturated hydrocarbon group with 23 to 40 carbon atoms. R 53 Each of these 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 greater than or equal to 0, b represents an integer greater than or equal to 1, and (a+b) is between 10 and 200. The use of silicone polymers as an additive, The auxiliary agent is a repeating unit derived from at least one water-repellent and oil-repellent monomer selected from fluorine-containing monomers (A1) and non-fluorine monomers (A2) having hydrocarbon groups with 7 to 40 carbon atoms, in an amount of 30 to 100% by weight relative to (A) the water-repellent and oil-repellent polymer. Use in a surface treatment agent containing a water-repellent and oil-repellent polymer having the properties of a water-repellent and oil-repellent polymer.

[0021]

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

[16] , comprising the above.

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

[16] to the substrate. [Effects of the Invention]

[0022] The surface treatment agent disclosed herein does not cause particle sedimentation, and polymers do not adhere to the rolls, preventing fabric staining. According to this disclosure, excellent water repellency, oil repellency, stain resistance, and dirt shedding properties, particularly water repellency, can be obtained. The water repellency, oil repellency, stain resistance, and dirt shedding properties are highly durable. The surface treatment agent disclosed herein provides the substrate with excellent slip resistance (excellent resistance to slipping). The surface treatment agents disclosed herein can be used as water-repellent and oil-repellent agents, antifouling agents, and / or stain removers. [Modes for carrying out the invention]

[0023] Surface treatment agents are generally aqueous emulsions or organic solvent solutions containing water- and oil-repellent polymers and silicone polymers. Surface treatment agents are (A) A water-repellent and oil-repellent polymer having repeating units derived from a water-repellent and oil-repellent monomer which is either a fluorine-containing monomer having a fluoroalkyl group (A1) or a non-fluorine monomer having a hydrocarbon group having 7 to 40 carbon atoms (i.e., a long-chain hydrocarbon group-containing non-fluorine monomer) (A2), or both. (B) Silicone polymer, and (C) Liquid media It consists of including.

[0024] (A) Water-repellent and oil-repellent polymer The water- and oil-repellent polymers are homopolymers having repeating units derived from fluorine-containing monomers having fluoroalkyl groups or non-fluorine monomers having hydrocarbon groups with 7 to 40 carbon atoms (i.e., long-chain hydrocarbon group-containing non-fluorine monomers), copolymers having repeating units derived from two or more monomers selected from fluorine-containing monomers having fluoroalkyl groups and long-chain hydrocarbon group-containing non-fluorine monomers, or copolymers having repeating units derived from other polymerizable compounds copolymerizable with repeating units derived from fluorine-containing monomers having fluoroalkyl groups or long-chain hydrocarbon group-containing non-fluorine monomers. Water- and oil-repellent polymers are either fluorine-containing polymers or non-fluorine polymers that do not contain fluorine atoms. Fluorine-containing polymers are polymers having repeating units derived from fluorine-containing monomers having fluoroalkyl groups, while non-fluorine polymers are polymers having repeating units derived from non-fluorine monomers containing long-chain hydrocarbon groups. The water- and oil-repellent polymer may be a random polymer or a block polymer.

[0025] In this disclosure, the water- and oil-repellent polymer (A) may consist only of (A1) repeating units derived from a fluorine-containing monomer having a fluoroalkyl group and / or (A2) repeating units derived from a long-chain hydrocarbon group-containing nonfluorine monomer, In addition to the repeating units (A1) and / or (A2), (A3) Repeating units derived from non-fluorine, non-crosslinkable monomers and (A4) Repeating units derived from non-fluorine, crosslinkable monomers, either or both. It is preferable that it has

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

[0027] (A1) Fluorine-containing monomer Fluorine-containing monomers are generally polymerizable compounds having a perfluoroalkyl group or perfluoroalkenyl group and an acrylic acid group, a methacrylic acid group, or an α-substituted acrylic acid group.

[0028] The fluorine-containing monomer (A1) is given by formula: CH2=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 compound represented by is preferably used.

[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 -(CH2) x -(where x is 1 to 10), or a group represented by the formula -R 2 (R 1 )N-SO2- or a group represented by the formula -R 2 (R 1 )N-CO- (where R 1 is an alkyl group having 1 to 10 carbon atoms, R 2 is a linear alkylene group or a branched alkylene group having 1 to 10 carbon atoms).), or a group represented by the formula -CH2CH(OR 3 )CH2-(Ar-O) p -(where R 3 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (for example, formyl or acetyl), Ar is an arylene group optionally having a substituent, and p represents 0 or 1.), or a group represented by the formula -CH2-Ar-(O) q -(where Ar is an arylene group optionally having a substituent and q is 0 or 1.), -(CH2) m -SO2-(CH2) n - group or -(CH2) m -S-(CH2) n - group (where m is 1 to 10 and n is 0 to 10) may be used. Specific examples of X 11 are H, CH3, Cl, Br, I, F, CN, CF3. 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: CH2=C(-X 11 )-C(=O)-Y 11 -Z 11 -Rf [wherein, 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, a CFX 1 X 2 group (wherein, X 1 and X 2 are each 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 cycloaliphatic group having 6 to 18 carbon atoms, a -CH2CH2N(R 1 )SO2- group (wherein, R 1 is an alkyl group having 1 to 4 carbon atoms), -CH2CH(OZ 1 )CH2-(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), -(CH2) n -Ph-O- group (wherein, Ph is a phenylene group and n is 0 to 10), -(CH2) m -SO2-(CH2) n - group or -(CH2) m -S-(CH2) 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.] Preferably, it is an acrylate ester or an acrylamide represented by the formula.

[0031] In fluorine-containing monomers, 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 Rf groups are -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -CF2CF2CF2CF3, -CF2CF(CF3)2, -C(CF3)3, -(CF2)4CF3, -(CF2)2CF(CF3)2, -CF2C(CF3)3, -CF(CF3)CF2CF2CF3, -(CF2)5CF3, -(CF2)3CF(CF3)2, -(CF2)4CF(CF3)2, and -C8F 17 And so on.

[0032] Z 11 This includes aliphatic groups with 1 to 10 carbon atoms, aromatic or cyclic aliphatic groups with 6 to 18 carbon atoms, and -CH2CH2N(R 1 )SO2- group (however, R 1 (This refers to an alkyl group having 1 to 4 carbon atoms.) -CH2CH(OZ 1 )CH2-(Ph-O) p -Base (however, Z 1 is a hydrogen atom or acetyl group, Ph is a phenylene group, and p is 0 or 1. ), -(CH2) n -Ph-O- group (where Ph is a phenylene group and n is 0-10), -(CH2) m -SO2-(CH2) n -Base or -(CH2) m -S-(CH2) n -The group is preferably a - group (where m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (particularly with 1 to 4 carbon atoms, for example 1 or 2). The aromatic group or cyclic aliphatic group may be substituted or unsubstituted. The S group or SO2 group may be directly bonded to the Rf group.

[0033] Specific examples of fluorine-containing monomers include, but are not limited to, the following. CH2=C(-H)-C(=O)-O-(CH2)2-Rf CH2=C(-H)-C(=O)-O-C6H4-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-Rf CH2=C(-H)-C(=O)-O-(CH2)2N(-CH3) SO2-Rf CH2=C(-H)-C(=O)-O-(CH2)2N(-C2H5) SO2-Rf CH2=C(-H)-C(=O)-O-CH2CH(-OH) CH2-Rf

[0034] CH2=C(-H)-C(=O)-O-CH2CH(-OCOCH3) CH2-Rf CH2=C(-H)-C(=O)-O-(CH2)2-S-Rf CH2=C(-H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-H)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-H)-C(=O)-NH-(CH2)2-Rf CH2=C(-CH3)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CH3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CH3)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CH3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CH3)-C(=O)-NH-(CH2)2-Rf

[0035] CH2=C(-F)-C(=O)-O-(CH2)2-S-Rf CH2=C(-F)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-F)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-F)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-F)-C(=O)-NH-(CH2)2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-S-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-Cl)-C(=O)-NH-(CH2)2-Rf

[0036] CH2=C(-CF3)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CF3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CF3)-C(=O)-NH-(CH2)2-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CF2H )-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-CF2H )-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CF2H )-C(=O)-NH-(CH2)2-Rf CH2=C(-CN)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CN)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CN )-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-CN )-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CN )-C(=O)-NH-(CH2)2-Rf

[0037] CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CF2CF3)-C(=O)-NH-(CH2)2-Rf CH2=C(-F)-C(=O)-O-(CH2)3-S-Rf CH2=C(-F)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-F)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-F)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH2=C(-F)-C(=O)-NH-(CH2)3-Rf

[0038] CH2=C(-Cl)-C(=O)-O-(CH2)3-S-Rf CH2=C(-Cl)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)3-S-Rf CH2=C(-CF3)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-CF2H )-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CF2H )-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf

[0039] CH2=C(-CN)-C(=O)-O-(CH2)3-S-Rf CH2=C(-CN)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-CN )-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CN )-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf [In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms.]

[0040] (A2) Long-chain hydrocarbon group-containing nonfluorine monomer Long-chain hydrocarbon group-containing non-fluorinated monomers do not contain fluoroalkyl groups. Long-chain hydrocarbon group-containing non-fluorinated monomers do not contain fluorine atoms. Long-chain hydrocarbon groups can be saturated or unsaturated. It is preferable that the long-chain hydrocarbon group be a saturated hydrocarbon group, particularly an alkyl group.

[0041] The long-chain hydrocarbon group is preferably a linear or branched hydrocarbon group having 7 to 40 carbon atoms. The number of carbon atoms in the linear or branched hydrocarbon group may be 10 to 40, 12 to 40, or 18 to 40. 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 a saturated aliphatic hydrocarbon group, particularly an alkyl group. The long-chain hydrocarbon group is particularly preferably a stearyl group, an eicosyl group, or a behenyl group.

[0042] Long-chain hydrocarbon group-containing nonfluorine monomers are given by formula: CH2=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 with 7 to 40 carbon atoms. n is an integer between 1 and 3. It is preferable that the monomer is represented by [the symbol shown].

[0043] X may be a hydrogen atom, a methyl group, a halogen 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, or a cyano group. Preferably, X is a hydrogen atom, a methyl group, or a chlorine atom.

[0044] Y is a divalent to tetravalent group. It is preferable that Y is a divalent group. Y is preferably a group composed of at least one of the following: a hydrocarbon group having one carbon atom, -C6H6-, -O-, -C(=O)-, -S(C=O)2-, or -NH- (excluding hydrocarbon groups). Examples of hydrocarbon groups having one carbon atom include -CH2-, -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 -(CH2) m -(m is an integer between 1 and 5) or -C6H6- (phenylene group). That is the case.

[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-, -O-C6H6-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H6-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m-NH-C(=O)-NH-, -NH-(CH2) m -O-C6H6-, -NH-(CH2) m -NH-C6H6- [In the formula, m is an integer between 1 and 5, in particular 2 or 4.] These are some examples.

[0047] Y is -O-, -NH-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH- [In the formula, m is an integer between 1 and 5, in particular 2 or 4.] It is even more preferable that Y is -O-(CH2) m It is particularly preferable that the form be -NH-C(=O)-.

[0048] Y is -O-, -NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH- [In the formula, m is an integer between 1 and 5, in particular 2 or 4.] It is particularly preferable that this be the case.

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

[0050] n is an integer between 1 and 3, preferably 1. When Y has a tetravalent C1 hydrocarbon group, n=3 is preferable. When Y has a trivalent C1 hydrocarbon group, n=2 is preferable. When Y does not have a trivalent or tetravalent C1 hydrocarbon group, n=1.

[0051] An example of a long-chain hydrocarbon group-containing nonfluorine monomer (A2) is: (a1) Acrylic monomers in which C(=O)-O- or C(=O)-NH- is directly bonded to a hydrocarbon group having 7 to 40 carbon atoms, and (a2) 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] Acrylic monomer (a2) is a different compound from 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 that 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 Acrylic monomer (a1) is given by formula: CH2=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 This refers to a hydrocarbon group with 7 to 40 carbon atoms. It is preferable that the compound is one shown in [the formula].

[0054] Acrylic monomer (a1) is Y1 A long-chain acrylate ester monomer in which is -O-, or Y 1 It is a long-chain acrylamide monomer with -NH-.

[0055] X 1 This may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. 1 Examples include hydrogen atoms, methyl groups, chlorine atoms, bromine atoms, iodine atoms, and cyano groups. 1 Preferably, these are hydrogen atoms, methyl groups, and chlorine atoms.

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

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

[0058] Specific examples of long-chain acrylate ester monomers include lauryl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, eicosyl α-chloroacrylate, and behenyl α-chloroacrylate. Specific examples of long-chain acrylamide monomers include lauryl(meth)acrylamide, stearyl(meth)acrylamide, icosyl(meth)acrylamide, and behenyl(meth)acrylamide. The presence of long-chain acrylate ester monomers or long-chain acrylamide monomers enhances the water-repellent, oil-repellent, and texture properties of the water-repellent 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. Acrylic monomer (a2) is given by formula: CH2=C(-X 2 )-C(=O)-Y 2 -Z 1 ( newZ 2 -R 2 ) p [where, X 2 is a hydrogen atom, a monovalent organic group, or a halogen atom. Y 2 is -O- or -NH-, Z 1 This is a directly bonded, divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms. Z 2 Each of these is a divalent to tetravalent linking group having at least one group selected from direct bonds, -O-, and -NH-, R 2 These are, independently, hydrocarbon groups having 7 to 40 carbon atoms. p is either 1 or 2. It is preferable that the compound is one shown in [the formula].

[0060] Acrylic monomer (a2) is Y 2 A long-chain acrylate ester monomer in which is -O-, or Y 2 It is a long-chain acrylamide monomer with -NH-.

[0061] X 2 This may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. 2 Examples include hydrogen atoms, methyl groups, chlorine atoms, bromine atoms, iodine atoms, and cyano groups. The less rigid the main chain of the resulting polymer, the less it inhibits the crystallinity of the side chains, so X 2It is 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 It is -O- or -NH-.

[0063] Z 1 This is a directly bonded, divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms (especially alkyl groups), and may have a branched structure. 1 The number of carbon atoms is preferably 2 to 4, and particularly preferably 2. 1 Specific examples include, as direct bonds and divalent groups, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, and those with branched structures (trivalent groups) -CH2CH=, -CH2(CH-)CH2-, -CH2CH2CH=, -CH2CH2CH2CH2CH=, -CH2CH2(CH-)CH2-, -CH2CH2CH2CH=. 1 It is preferable that the bonding is not direct.

[0064] Z 2 Specific examples include direct bonding, -O-, -NH-, and -(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 -C6H6-, -(O) k -(CH2) m -O-, -NH-(CH2) m -NH-, -(O) k -(CH2) m -NH-, -NH-(CH2) m -O-, -(O) k -(CH2) m -OC(=O)-, -(O) k -(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m-C(=O)-O-, -(O) k -(CH2) m -OC(=O)-NH-, -(O) k -(CH2) m -NH-C(=O)-O-, -(O) k -(CH2) m -C(=O)-NH-, -(O) k -(CH2) m -NH-C(=O)-, -(O) k -(CH2) m -NH-C(=O)-NH-, -(O) k -(CH2) m -O-C6H6-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H6-, -NH-(CH2) m -NH-C6H6- [wherein k is 0 or 1, and m is an integer from 1 to 5, in particular 2 or 4].

[0065] Z 2 is, -(O) k -, -NH-, -(O) k -(CH2) m -OC(=O)-, -(O) k -(CH2) m -NH-C(=O)-, -(O) k -(CH2) m -OC(=O)-NH-, -(O) k -(CH2) m -NH-C(=O)-O-, -(O) k -(CH2) m -NH-C(=O)-NH- [In the formula, k is either 0 or 1, and m is an integer between 1 and 5, in particular 2 or 4.] It is particularly preferable that this be the case.

[0066] Z 1 and Z 2 They cannot be directly bonded at the same time.

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

[0068] Acrylic monomer (a2) is CH2=C(-X 2 )-C(=O)-O-(CH2) m -NH-C(=O)-R 2 CH2=C(-X 2 )-C(=O)-OR 2 Or, preferably, a combination of these [where X 2 , m and R 2 This is equivalent to the above. ]. Acrylic monomer (a2) is CH2=C(-X 2 )-C(=O)-O-(CH2) m -NH-C(=O)-R 2 It is particularly preferable that this be the case.

[0069] Acrylic monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of long-chain alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate. Alternatively, the acrylic monomer (a2) can also be produced by reacting a (meth)acrylate having an isocyanate group in its side chain, such as 2-methacryloyloxyethyl isocyanate, with a long-chain alkylamine or 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 acrylic monomer (a2) are as follows. The compounds with the following chemical formulas are acrylates in which the α-position is a hydrogen atom, but specific examples may include methacrylates in which the α-position is a methyl group and acrylates in which the α-position is a chlorine atom. TIFF0007845919000012.tif2044

[0071] TIFF0007845919000013.tif2152 TIFF0007845919000014.tif2253 TIFF0007845919000015.tif2153

[0072] TIFF0007845919000016.tif2357 TIFF0007845919000017.tif2357 TIFF0007845919000018.tif2361

[0073] TIFF0007845919000019.tif2563 TIFF0007845919000020.tif2363

[0074] TIFF0007845919000021.tif2966 TIFF0007845919000022.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 in which the α-position is a methyl group and acrylate in which the α-position is a chlorine atom.

[0075] Typical specific examples of the acrylic monomer (a2) are amidoethyl palmitate (meth)acrylate, amidoethyl stearate (meth)acrylate, amidoethyl behenate (meth)acrylate, and amidoethyl myristate (meth)acrylate.

[0076] [[ID=^11]]The acrylic monomer (a2) has the formula: R 22 %-C(=O)-NH-R 23 -O-R 21 [In the formula, R 21 is 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.] It is particularly preferable that it is an amide group-containing monomer represented by

[0077] R 21 is an organic residue having an ethylenically unsaturated polymerizable group and is not particularly limited if there is a double bond between carbons. Specifically, -C(=O)CR 24 =CH2, -CHR 24 =CH2, -CH2CHR 24 =CH2 and other organic residues having an ethylenically unsaturated polymerizable group are exemplified, and R 24 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Also, R 21 may have various organic groups other than the ethylenically unsaturated polymerizable group. For example, organic groups such as chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups are exemplified, and these organic groups may be substituted with various substituents. R 21 is preferably -C(=O)CR 24 =CH2. R22 This is a hydrocarbon group having 7 to 40 carbon atoms, preferably an alkyl group, and includes chain hydrocarbons, cyclic hydrocarbons, etc. Among these, it is preferably a chain hydrocarbon, and particularly preferably a linear saturated hydrocarbon group. 21 The number of carbon atoms is 7 to 40, preferably 11 to 27, and particularly preferably 15 to 23. R 23 This 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 linear or branched, and may have unsaturated bonds, but linear is preferred. 23 The number of carbon atoms is preferably 2 to 4, and particularly preferably 2. 23 It is preferable that it is an alkylene group.

[0078] Amide group-containing monomers are R 21 Something that is on its own (for example, R 21 (Only compounds with 17 carbon atoms), or R 21 Those that are multiple combinations (for example, R 21 A compound with 17 carbon atoms and R 21 It may be a mixture of a compound having 15 carbon atoms.

[0079] An example of an amide group-containing monomer is carboxylic acid amide alkyl (meth)acrylate. Specific examples of amide group-containing monomers include palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, beheninic acid amidoethyl (meth)acrylate, myristateic acid amidoethyl (meth)acrylate, lauric acid amidoethyl (meth)acrylate, isostearate ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tert-butylcyclohexylcaproic acid amidoethyl (meth)acrylate, adamantane carboxylic acid ethyl amide (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 stearamide ethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamide ethyl (meth)acrylate. In a mixture containing stearamide ethyl (meth)acrylate, the amount of stearamide ethyl (meth)acrylate may be, for example, 55 to 99% by weight, preferably 60 to 85% by weight, and more preferably 65 to 80% by weight, relative to the total weight of the amide group-containing monomer, and the remaining monomer may be, for example, palmitate ethyl (meth)acrylate.

[0081] (A3) Non-fluorine, non-crosslinkable monomer Non-fluorinated, non-crosslinkable monomers (A3) are monomers other than long-chain hydrocarbon group-containing non-fluorinated monomers (A2). Non-fluorinated, non-crosslinkable monomers (A3) are monomers that do not contain fluorine atoms. Non-fluorinated, non-crosslinkable monomers (A3) do not have crosslinkable functional groups. Non-fluorinated, non-crosslinkable monomers (A3) are non-crosslinkable, unlike crosslinkable monomers (A4). Non-fluorinated, non-crosslinkable monomers (A3) are preferably non-fluorinated monomers having an ethylenically unsaturated carbon-carbon double bond. Non-fluorinated, non-crosslinkable monomers (A3) are preferably vinyl monomers that do not contain fluorine. Non-fluorinated, non-crosslinkable monomers (A3) are generally compounds having one ethylenically unsaturated carbon-carbon double bond.

[0082] A preferred non-fluorine, non-crosslinkable monomer (A3) is given by formula: CH2=CA-T [In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom), T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 40 carbon atoms, or a chain or cyclic organic group having 1 to 41 carbon atoms and possessing an ester bond. It is a compound represented by [the formula shown].

[0083] Examples of chain-like or cyclic hydrocarbon groups having 1 to 40 carbon atoms include straight-chain 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 linear or cyclic organic groups having 1 to 41 carbon atoms and containing ester bonds are -C(=O)-OQ and -OC(=O)-Q (where 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 non-fluorinated, non-crosslinkable monomers (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 ethers. Non-fluorinated, non-crosslinkable monomers (A3) are not limited to these examples.

[0086] The non-fluorine, non-crosslinkable monomer (A3) may be a (meth)acrylate ester having an alkyl group. The number of carbon atoms in the alkyl group may be 1 to 17. For example, the non-fluorine, non-crosslinkable monomer (A3) has the general formula: CH2=CA 1 COOA 2 [In the formula, A 1 This is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom, and an iodine atom). A 2 C n H 2n+1 This is an alkyl group represented by (n=1~17). It may be an acrylate as shown. The fluorine-containing monomer does not necessarily have to have repeating units derived from (meth)acrylate esters having an alkyl group with 1 to 17 carbon atoms.

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

[0088] Specific examples of cyclic hydrocarbon groups include cyclohexyl group, t-butylcyclohexyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, and adamantyl group. The acrylate group is preferably an acrylate group or a methacrylate group, but a methacrylate group is particularly preferred. Specific examples of monomers having cyclic hydrocarbon groups 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 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 atoms, bromine atoms or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide.

[0090] (A4) Non-fluorine 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 are a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, etc.

[0091] Examples of the non-fluorine 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, glycidyl (meth)acrylate, etc.

[0092] By copolymerizing a non-fluorine, non-crosslinked monomer (A3) and / or a non-fluorine, crosslinked monomer (A4), various properties such as water and oil repellency, stain resistance, cleaning resistance, washability, solvent solubility, hardness, and feel can be improved as needed.

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

[0094] Polymers having blocked isocyanate groups are obtained by polymerizing monomers in the presence of a blocked isocyanate compound. The blocked isocyanate compound is an isocyanate blocked by 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] Polymers having siloxane groups are obtained by polymerizing monomers in the presence of organopolysiloxane compounds (e.g., mercapto-functional organopolysiloxanes, vinyl-functional organopolysiloxanes). In one embodiment, the mercapto-functional organopolysiloxane has siloxy units having the following average formula: (R2SiO) a (RR N SiO) b (RR S SiO) c [In the formula, a is between 0 and 4000, or between 0 and 1000, or between 0 and 400, b is 1 to 1000, or 1 to 100, or 1 to 50. c is between 1 and 1000, or between 1 and 100, or between 1 and 50; R is independently a monovalent organic group, Alternatively, R is a hydrocarbon with 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 It is a monovalent amino-functional organic group, R S This is a monovalent mercapto-functional organic group.

[0096] The following are particularly preferred combinations of monomers in water- and oil-repellent polymers. Fluorine-containing monomer (A1) + non-fluorine monomer (A2) (especially 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 monomer (A2-i) + acrylamide monomer (A2-iv) In the above combination, it is preferable to further include a halogenated olefin.

[0097] The respective amounts of the fluorine-containing monomer (A1) and the long-chain hydrocarbon group-containing nonfluorine monomer (A2) (or the total of monomers (A1) and monomer (A2)) (where the total of monomers (A1) and 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, relative to the water-repellent and oil-repellent polymer. In a water-repellent and oil-repellent polymer, with respect to 100 parts by weight of a total of a fluorine-containing monomer (A1) and a long-chain hydrocarbon group-containing nonfluorine monomer (A2), The amount of non-fluorine, non-crosslinkable monomer (A3) is 1000 parts by weight or less, for example, 0.1 to 300 parts by weight, and especially 1 to 200 parts by weight. The amount of non-fluorine crosslinkable monomer (A4) may be 50 parts by weight or less, for example, 30 parts by weight or less, and particularly 0.1 to 20 parts by weight. The amount of non-fluorine, 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, relative to the water-repellent and oil-repellent polymer (or the sum of monomers (A1), monomer (A2), and monomer (A3)).

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

[0099] (B) Silicone polymer Silicone polymers are, formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )(R 52 )-O-] b -Si(R 53 )3 [In the formula, R 51 Each of these 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 of these independently represents a saturated hydrocarbon group with 23 to 40 carbon atoms. R 53 Each of these 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 greater than or equal to 0, b represents an integer greater than or equal to 1, and (a+b) is between 5 and 200. It is a polymer represented by [the formula shown].

[0100] R 51 and R 53 In this, 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 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group; phenyl group, tolyl group, naphthyl group, or groups in which some or all of the hydrogen atoms bonded to these groups are substituted with halogen atoms, amino groups, cyano groups, etc. 51 and R 53 It is preferable that this is a methyl group or an ethyl group. R 51 and R 53 It 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 this context, the alkoxy group having 1 to 4 carbon atoms may be linear or branched. Examples of alkoxy groups having 1 to 4 carbon atoms include the methoxy group, ethoxy group, propoxy group, and butoxy group.

[0101] In terms of being easy to manufacture industrially and readily available, R 51 and R 53 It 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 saturated hydrocarbon groups having 23 to 40 carbon atoms include the tricosyl group (23 carbon atoms), lignoceryl group (tetracosyl group, 24 carbon atoms), cellotyl group (hexacosyl group, 26 carbon atoms), montyl group (octacosyl group, 28 carbon atoms), merisyl group (triacontane group, 30 carbon atoms), and dotriacontane group (32 carbon atoms).

[0103] a is a non-negative integer. In terms of ease of industrial manufacture and availability, a is preferably 40 or less, and more preferably 30 or less.

[0104] The sum of a and b is between 5 and 200. Preferably, the sum of a and b is between 10 and 100, and more preferably between 40 and 60, in terms of ease of industrial manufacture, availability, and handling. a may be between 0 and 150, for example, 1 and 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] If a or b is 2 or more, there are multiple R 51 and R 52 Each of these may be the same or different. R 51 and R 52 Base and R 53 It is preferable that 50 mol% or more of the total number of groups are methyl groups. The order of existence of the repeating units enclosed by a or b is not limited to the order shown in the chemical formula, but is arbitrary. That is, the silicone polymer may be a random polymer or a block polymer.

[0106] Examples of silicone polymers are as follows: TIFF0007845919000023.tif2371[In the formula, a represents an integer from 0 to 150, b represents an integer between 1 and 150. (a+b) is between 5 and 200. n is an integer between 19 and 36.

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

[0108] Silicone polymers can be synthesized by conventionally known methods. For example, a silicone polymer can be obtained by hydrosilylation of an α-olefin with a silicone having SiH groups.

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

[0110] α-olefins are compounds that give rise to saturated hydrocarbon groups with 23 to 40 carbon atoms in silicone polymers. Specific examples of α-olefins include 1-tricocene, 1-tetracosene, 1-hexacocene, 1-octacosene, 1-triaconthene, and 1-dotriaconthene. The hydrosilylation reaction may be carried out by reacting the α-olefin with the SiH group-containing silicone in a stepwise or one-time manner, if necessary, in the presence of a catalyst.

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

[0112] Examples of catalysts used in hydrosilylation reactions include compounds such as platinum and palladium, with platinum compounds being preferred. Examples of platinum compounds include platinum(IV) chloride.

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

[0114] (C) Liquid media The water-repellent composition contains a liquid medium. The liquid medium is an organic solvent, or water, an organic solvent, or a mixture of water and an organic solvent. Water-repellent compositions are generally in the form of solutions or dispersions. A solution is a solution in which the polymer is dissolved in an organic solvent. A dispersion is an aqueous dispersion in which the polymer is dispersed in an aqueous medium (water, or a mixture of water and an organic solvent).

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

[0116] (D) Surfactants When the water-repellent composition is an aqueous dispersion, it is preferable that it contains a surfactant. In a water-repellent composition, the surfactant includes a nonionic surfactant. Furthermore, it is preferable that the surfactant 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. Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0118] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1-6 valent (especially 2-5 valent) alcohols with 1-50 carbon atoms (especially 10-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms. Examples of ester ethers are compounds formed by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are 1-6 valent (especially 2-5 valent) alcohols with 1-50 carbon atoms (especially 3-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0119] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolaminos. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups. Polyhydric alcohols may be divalent to pentavalent alcohols with 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (a secondary amine or preferably a tertiary amine) (for example, having 5 to 50 carbon atoms).

[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 of the oxyalkylene group is preferably 2 to 10. In general, the number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100. Nonionic surfactants are selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and are preferably nonionic surfactants having an oxyalkylene group.

[0121] Nonionic surfactants may be alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycol esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene oxide adducts of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide adduct and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (which may be random copolymers or block copolymers) are preferred. Furthermore, nonionic surfactants are preferable because they do not contain aromatic groups due to environmental concerns (biodegradability, endocrine disruptors, etc.).

[0122] Nonionic surfactants are defined by the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 This 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 of these is independently identical or distinct, an alkylene group having 3 or more carbon atoms (e.g., 3 to 10). R 3 These are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms. p is a number greater than or equal to 2. q is a number greater than or equal to 1, or 0. It may be a compound represented by [the formula shown].

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

[0124] Specific examples of nonionic surfactants include ethylene oxide, hexylphenol, isooctatylphenol, hexadecanol, oleic acid, and alkanes (C 12 -C 16 ) Thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl(C 12 -C 18 This includes condensation products with amines, etc.

[0125] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example, 30 to 75% by weight, and especially 40 to 70% by weight, relative to the molecular weight of the nonionic surfactant (copolymer). The average molecular weight of nonionic surfactants is generally between 300 and 5,000, for example, between 500 and 3,000. Nonionic surfactants may be a mixture of compounds with an HLB (hydrophilic-hydrophobic balance) of less than 15 (especially 5 or less) and compounds with an HLB of 15 or more. An example of a compound with an HLB of less than 15 is sorbitan fatty acid ester. An example of a compound with an HLB of 15 or more is polyoxyethylene alkyl ether. The weight ratio of the compound with an HLB of less than 15 to the compound with an HLB of 15 or more may be 90:10 to 20:80, for example, 85:15 to 55:45. Nonionic surfactants may be a single type or a mixture of two or more types.

[0126] (D2) Cationic surfactant The cationic surfactant is preferably a compound that does not have an amide group.

[0127] Cationic surfactants may be amine salts, quaternary ammonium salts, or oxyethylene-added ammonium salts. Specific examples of cationic surfactants are not limited to alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt-type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and quaternary ammonium salt-type surfactants such as benzethonium chloride.

[0128] Preferred examples of cationic surfactants are: R 21 -N + (-R 22 )(-R 23 )(-R 24 ) X - [In the formula, R 21 , R 22 , R 23 and R 24 These are hydrocarbon groups with 1 to 40 carbon atoms. X is an anionic group. It is a compound of [the compound]. R 21 , R 22 , R 23 and -R 24 Specific examples of X are alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid, acetic acid). The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl group with 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 (for example, C12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 These are H or C1-C4 alkyl groups, benzyl groups, and polyoxyethylene groups (number of oxyethylene groups e.g., 1 (especially 2, especially 3) to 50). (CH3 and C2H5 are particularly preferred.) X is a halogen atom (for example), a C1-C4 fatty acid base, p is either 1 or 2, q is either 2 or 3, and p + q = 4. It may be an ammonium salt represented by R. 1 The number of carbon atoms can be 12 to 50, for example, 12 to 30.

[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, amide betaines, and betaine acetate. Specifically, examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amidopropyl dimethylaminoacetic acid betaine.

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

[0133] (E) Other ingredients The surface treatment agent may contain, in addition to the water- and oil-repellent polymer, liquid medium, and surfactant, at least one of a non-fluorine water-repellent compound and an additive. (E1) Non-fluorinated water-repellent compound Surface treatment agents may contain water-repellent compounds that do not contain fluorine atoms (non-fluorine water-repellent compounds). 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] Nonfluorinated acrylate polymers are homopolymers composed of one type of nonfluorinated acrylate monomer, copolymers composed of at least two types of nonfluorinated acrylate monomers, or copolymers composed of at least one type of nonfluorinated acrylate monomer and at least one other type of nonfluorinated monomer (ethylenically unsaturated compound, e.g., ethylene, vinyl monomers). The non-fluorinated acrylate monomers that constitute the non-fluorinated acrylate polymer are given by formula: CH2=CA-T [In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom), T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 40 carbon atoms, or a chain or cyclic organic group having 1 to 41 carbon atoms and possessing an ester bond. It is a compound represented by [the formula shown].

[0135] Examples of chain-like or cyclic hydrocarbon groups having 1 to 40 carbon atoms include straight-chain 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 linear or cyclic organic groups having 1 to 41 carbon atoms and containing ester bonds are -C(=O)-OQ and -OC(=O)-Q (where 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 non-fluorinated acrylate monomers include alkyl (meth)acrylates, polyethylene glycol (meth)acrylates, polypropylene glycol (meth)acrylates, methoxypolyethylene glycol (meth)acrylates, and methoxypolypropylene glycol (meth)acrylates.

[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 (for example, 10 to 30). Specific examples of non-fluorinated acrylate monomers are lauryl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate. Non-fluorinated acrylate polymers can be produced using the same polymerization methods as water- and oil-repellent polymers.

[0139] A saturated or unsaturated hydrocarbon compound is preferably a saturated hydrocarbon. In a saturated or unsaturated hydrocarbon compound, the number of carbon atoms may be 15 or more, preferably 20 to 300, for example, 25 to 100. A specific example of a saturated or unsaturated hydrocarbon compound is paraffin. Silicone compounds are generally used as water repellents. The term "silicone compound" is not limited to any compound that exhibits water repellency. 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, and especially 5 to 100 parts by weight, per 100 parts by weight of the water-repellent and oil-repellent polymer.

[0140] (E2) additive The surface treatment agent may contain additives. Examples of additives include silicon-containing compounds, waxes, and acrylic emulsions. Other examples of additives include other fluorine-containing polymers, drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, surfactants, antifreezes, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, defoamers, texture modifiers, lubricity modifiers, antistatic agents, hydrophilic agents, antibacterial agents, preservatives, insecticides, fragrances, and flame retardants.

[0141] The water- and oil-repellent polymers in this disclosure can be produced by any conventional polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

[0142] In solution polymerization, a method is employed in which monomers are dissolved in an organic solvent in the presence of a polymerization initiator, followed by nitrogen purging, and then heating and stirring at a temperature of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators 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, per 100 parts by weight of monomer.

[0143] Organic solvents are inert to monomers and dissolve them, and may include, for example, esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), and alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically isopropyl alcohol). Specific examples of organic solvents include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, 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, per 100 parts by weight of the total monomers.

[0144] In emulsion polymerization, monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and then polymerized by stirring at a temperature of 50-80°C for 1-10 hours after nitrogen purging. Polymerization initiators include water-soluble ones 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, as well as oil-soluble ones such as 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 0.01-10 parts by weight per 100 parts by weight of monomer.

[0145] To obtain a polymer aqueous dispersion with excellent stability during storage, it is desirable to polymerize the monomers by micronizing them in water using an emulsifying device that can impart strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer. Various emulsifiers, including anionic, cationic, and nonionic types, can be used as emulsifiers, typically in an amount ranging from 0.5 to 20 parts by weight per 100 parts by weight of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely miscible, it is preferable to add a compatibilizer that allows them to be sufficiently miscible, such as a water-soluble organic solvent or a low molecular weight monomer. Adding a compatibilizer can improve emulsification and copolymerization properties.

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

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

[0148] The treatment agent of this 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 ingredient of the surface treatment agent) and a medium (particularly a liquid medium, e.g., 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, relative to the treatment agent. In the treatment agent, the concentration of the water-repellent 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 disclosed herein can be applied to a workpiece by conventionally known methods. Typically, the treatment agent is dispersed and diluted in an organic solvent or water, and then applied to the surface of the workpiece by known methods such as immersion coating, spray coating, or foam coating, followed by drying. If necessary, it may also be applied together with a suitable crosslinking agent (e.g., blocked isocyanate) and curing may be performed. Furthermore, it is possible to use the treatment agent disclosed herein in combination with insecticides, softeners, antibacterial agents, flame retardants, antistatic agents, paint fixatives, wrinkle inhibitors, etc. The concentration of the water- and oil-repellent polymer in the treatment solution that comes into contact with the substrate may be 0.01 to 10% by weight (especially in the case of immersion coating), for example, 0.05 to 10% by weight.

[0150] Examples of materials to be treated with the treatment agents of the present disclosure (e.g., water- and oil-repellent agents) include textile products, stone materials, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Various examples of textile products can be given. For example, natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or blends thereof.

[0151] Textile products may be in any form, such as fibers or cloth. The processing agent disclosed herein can also be used as an internal or external release agent.

[0152] Water- and oil-repellent polymers can be applied to fibrous substrates (e.g., textile products) by any known method for treating textile products with a liquid. When the textile product is a cloth, the cloth may be immersed in the solution, or the solution may be applied to or sprayed onto the cloth. The treated textile product is dried and preferably heated, for example, at 100°C to 200°C, in order to exhibit oil repellency.

[0153] Alternatively, the water- and oil-repellent polymer may be applied to textile products by cleaning methods, for example, in washing or dry cleaning.

[0154] The textile products to be processed are typically cloths, including woven, knitted and nonwoven fabrics, cloths in garment form and carpets, but may also be fibers or yarns or intermediate textile products (e.g., slivers or rovings). The textile material may be natural fibers (e.g., cotton or wool), chemical fibers (e.g., viscose rayon or reocell), or synthetic fibers (e.g., polyester, polyamide or acrylic fibers), or a mixture of fibers (e.g., a mixture of natural and synthetic fibers). The water- and oil-repellent polymers of this disclosure are particularly effective in making cellulosic fibers (e.g., cotton or rayon) oleophobic and oil-repellent. The methods of this disclosure also generally make textile products hydrophobic and water-repellent.

[0155] Alternatively, the fibrous substrate may be leather. The water- and oil-repellent polymer may be applied to the leather in the form of an aqueous solution or aqueous emulsion at various stages of leather processing, for example, during the wetting process or during the finishing process, in order to make the leather hydrophobic and oil-repellent. Alternatively, the fibrous substrate may be paper. The water- and oil-repellent polymer may be applied to pre-formed paper, or it may be applied at various stages of papermaking, for example, during the drying period of the paper.

[0156] "Treatment" refers to applying a treatment agent to an object to be treated by means of immersion, spraying, coating, etc. Through treatment, the polymer, which is the active ingredient of the treatment agent, penetrates into the interior 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, percentages, or ratios refer to parts by weight, weight percentages, or weight ratios, unless otherwise specified. The examination procedure is as follows:

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

[0159] TIFF0007845919000024.tif41130

[0160] High water repellency test During testing using the spray method of JIS-L-1092 (AATCC-22), the ease with which water repelled upon contact with the fabric and the speed at which it flowed off the fabric were visually evaluated. The results are expressed by a water repellency score, as shown in the table below. A higher score indicates better water repellency.

[0161] TIFF0007845919000025.tif73160

[0162] Washing durability test The water repellency of the test fabric was evaluated after being washed 10 times and then dried in a tumble dryer (60°C for 30 minutes) in accordance with JIS L-0217 103.

[0163] Slip resistance test The slip resistance test was conducted according to JIS-L-1096 Method B. Five 10cm x 17cm test pieces were taken from a water-repellent treated polyester cloth (white) in both the warp and weft directions. Each test piece was folded in half with the right side facing inward, the fold was cut, and a straight stitch was sewn 1cm from the cut edge using a standard sewing machine needle with a thread of 78dex x 3 polyester filament, 5 stitches / cm. Using a tensile testing machine, a predetermined load (49.0N (5kgf)) was applied using the grab method with a gripping distance of 7.62cm and a tensile strength of 30cm per minute. After removing the test piece from the grips and leaving it for 1 hour, the size of the largest hole in the slippage load at which the slack near the seam disappeared was visually observed. The evaluation was as follows: "○" for almost no holes, "△" for small holes, and "×" for many holes.

[0164] Water dispersion stability The aqueous dispersion was left to stand at room temperature, and the presence or absence of separated solid matter was visually observed and evaluated according to the following criteria. ○: Uniform △: Separation / Small amount of solid matter present ×: Separation and presence of many solid particles

[0165] Gum Up Review A 1000g test solution was prepared using water with a hardness of 16 so that the solid content concentration of the aqueous dispersion was 1.8%, and it was placed in a pad that could be temperature-controlled to 40°C. A 20cm wide and 80cm long polyester cloth was made into a loop on the mangle to allow for continuous processing, and continuous processing was performed for 1 hour at a mangle pressure of 0.4 MPa. After 1 hour, the amount of solid matter adhering to the mangle was observed visually and by touch and evaluated according to the following criteria. ○: No solid matter at all △: Contains some solid material ×: Contains a lot of solids

[0166] Antifoaming performance evaluation A test solution was prepared by mixing a polymer dispersion with water with a hardness of 43 to achieve a solid content concentration of 0.3%, and then heating it to 40°C. 20 L / min of air was bubbled into the test solution for 10 minutes, and the foam height (in mm) was measured.

[0167] Texture evaluation Five evaluators conducted a sensory evaluation on a five-point scale, and the average of their results was taken. 5: Very soft 4: Soft 3: Untreated cloth 2: Hard 1: Very hard

[0168] Chalk Mark Evaluation After pressing a plastic rod with a 5mm diameter tip against the treated cloth and tracing the marks, the presence or absence of traces on the cloth was visually observed and evaluated on a 5-point scale as described below. 5: No traces whatsoever 4: Almost no traces are found. 3: Some traces are visible. 2: Traces are found 1: Clear traces are visible.

[0169] Synthesis Example 1 [Synthesis of C18URA (stearyl group-containing urethane acrylate)] TIFF0007845919000026.tif2152

[0170] 80.2g of hydroxyethyl acrylate, 100g of ethyl acetate, 0.03g of polymerization inhibitor, and 0.03g of tin catalyst were placed in a 1L four-necked flask. A stirring rod, thermometer, and reflux tube were set up, and 201.4g of octadecyl isocyanate was dissolved in 100g of ethyl acetate and placed in a dropping funnel. The dropping funnel was placed in the flask, and the temperature was raised to 70°C. The ethyl acetate solution of octadecyl isocyanate was gradually added dropwise from the dropping funnel over about 30 minutes, taking care to avoid exothermic reactions. After the addition was complete, the reaction was allowed to continue for another 2 hours. The reaction was terminated when the isocyanate peak disappeared by infrared spectroscopy (IR). The reactants were reprecipitation in methanol, washed with methanol, and dried under reduced pressure to obtain a white powder. 1 It was identified as C18URA by 1H-NMR. The melting point of the compound was found to be approximately 73°C using differential scanning calorimetry (DSC).

[0171] Synthesis Example 2 [Synthesis of C18ureaA (stearyl group-containing urea acrylate)] TIFF0007845919000027.tif2153

[0172] 200g of stearylamine, 100g of ethyl acetate, and 0.03g of polymerization inhibitor were placed in a 1L four-necked flask. A stirring rod, thermometer, and reflux tube were set up, and 2-acryloyloxyethyl isocyanate was dissolved in 100g of ethyl acetate and placed in a dropping funnel. The dropping funnel was placed in the flask, and the ethyl acetate solution of 2-acryloyloxyethyl isocyanate was gradually added dropwise from the dropping funnel over about 30 minutes, taking care to avoid exothermic reactions. After the addition was complete, the reaction was allowed to continue for another 2 hours. The reaction was terminated after confirming that the isocyanate peak had disappeared by infrared spectroscopy (IR). The reaction product was reprecipitation in methanol, washed with methanol, and dried under reduced pressure to obtain a white powder. 1 It was identified as C18UreaA by 1H-NMR. The melting point of the compound was found to be approximately 83°C by differential scanning calorimetry (DSC).

[0173] Synthesis Example 3 [Synthesis of C18ureaMA (stearyl group-containing urea methacrylate)] TIFF0007845919000028.tif3959(n=18)

[0174] 200g of stearylamine, 100g of ethyl acetate, and 0.03g of polymerization inhibitor were placed in a 1L four-necked flask. A stirring rod, thermometer, and reflux tube were set up, and 2-methacryloyloxyethyl isocyanate was dissolved in 100g of ethyl acetate and placed in a dropping funnel. The dropping funnel was placed in the flask, and the ethyl acetate solution of 2-methacryloyloxyethyl isocyanate was gradually added dropwise from the dropping funnel over about 30 minutes, taking care to avoid exothermic reactions. After the addition was complete, the reaction was allowed to continue for another 2 hours. The reaction was terminated after confirming that the isocyanate peak had disappeared by infrared spectroscopy (IR). The reaction product was reprecipitation in methanol, washed with methanol, and dried under reduced pressure to obtain a white powder. 1 It was identified as C18ureaMA by 1H-NMR. Differential scanning calorimetry (DSC) determined that the compound has a melting point of approximately 91°C.

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

[0176] Manufacturing Examples 2-7 Polymerization was carried out using the same method as in Production Example 1 with the compositions shown in Table 1 to obtain polymers. After obtaining the polymers, they were diluted with toluene to prepare toluene solutions 2-7 with a solid content of 20%.

[0177] Manufacturing Example 8 Add methyl hydrogen silicone oil to a 200 mL four-necked flask. 112 g of SiH:SiCH3 (molar ratio = 60:40, as measured by 1H NMR) and 0.02 g of hydrosilylated Pt catalyst were charged. A stirring rod, thermometer, and reflux tube were set up, and 36 g of CH2=CH-(CH2CH2)n-CH2CH3 (n=11) was placed in a dropping funnel. CH2=CH-(CH2CH2)n-CH2CH3 (n=11) was added dropwise from the dropping funnel while maintaining a temperature of 70 degrees Celsius. After the addition was complete, the reaction was continued at 70 degrees Celsius for about 3 hours. The disappearance of the SiH peak was confirmed by infrared spectroscopy (IR), and silicone polymer 6 was obtained.

[0178] Manufacturing examples 9-10 Silicone polymers 9-10 were obtained by synthesizing them using the same method as in Production Example 8 with the compositions shown in Table 2.

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

[0180] Manufacturing Example 11 In a 500ml poly 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. The mixture was heated to 60°C, stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed using ultrasound for 15 minutes. The emulsion dispersion was transferred to a 500ml autoclave, purged with nitrogen, and then 0.2g of lauryl mercaptan (LSH) and 20g of vinyl chloride were charged. 1g of azo group-containing water-soluble initiator was added, and the mixture was heated to 60°C and reacted for 4 hours to obtain an aqueous dispersion of the polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion 9 with a solid content of 20%.

[0181] Manufacturing examples 12, 14 Polymerization was carried out using the same method as in Production Example 11 with the compositions shown in Table 3 to obtain polymers. After that, the polymers were further diluted with pure water to prepare aqueous dispersions 12 and 14 with a solid content of 30%.

[0182] Manufacturing examples 15-18, 20-22 Polymerization was carried out in the same manner as in Production Example 11, except that the compositions shown in Table 3 were prepared and heated to 80°C. After obtaining the polymers, they were further diluted with pure water to prepare aqueous dispersions 15-18 and 20-22 with a solid content of 30%.

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

[0184] Manufacturing example 19 Polymerization was carried out in the same manner as in Production Example 13, except that the mixture was prepared with the composition shown in Table 3 and heated to 80°C. After obtaining the polymer, it was further diluted with pure water to prepare an aqueous dispersion 19 with a solid content of 30%.

[0185] Manufacturing Example 23 In a 250 ml poly container, 28 g of silicone polymer 8, 5.6 g of water-soluble glycol solvent, 60 g of pure water, 1.7 g of sorbitan fatty acid ester (HLB 5 or less), 0.7 g of polyoxyethylene alkyl ether (HLB 15 or more), and 0.6 g of cationic emulsifier were charged. The mixture was heated to 75°C, stirred for 1 minute at 2000 rpm with a homomixer, and then emulsified and dispersed using ultrasound for 10 minutes to obtain an aqueous dispersion. Subsequently, pure water was added to prepare an aqueous dispersion 23 with a solid content of 30%.

[0186] Manufacturing examples 24-25 After obtaining an aqueous dispersion with the composition shown in Table 4 using the same method as in Production Example 23, it was further diluted with pure water to prepare aqueous dispersions 24-25 with a solid content of 30%.

[0187] Comparative manufacturing example 6 In a 250 ml poly container, 28 g of comparative silicone polymer 1, 5.6 g of water-soluble glycol solvent, 60 g of pure water, 1.7 g of sorbitan fatty acid ester (HLB 5 or less), 0.7 g of polyoxyethylene alkyl ether (HLB 15 or more), and 0.6 g of cationic emulsifier were charged. The mixture was heated to 75°C, stirred for 1 minute at 2000 rpm with a homomixer, and then emulsified and dispersed using ultrasound for 10 minutes to obtain an aqueous dispersion. Subsequently, pure water was added to prepare comparative aqueous dispersion 6 with a solid content of 30%.

[0188] Comparative manufacturing examples 7-13 After obtaining an aqueous dispersion with the composition shown in Table 4 using the same method as in Comparative Production Example 6, the dispersion was further diluted with pure water to prepare comparative aqueous dispersions 7-13 with a solid content of 30%.

[0189] The meanings of the abbreviations are as follows: TIFF0007845919000029.tif73147

[0190] [Table 1]

[0191] [Table 2]

[0192] [Table 3]

[0193] [Table 4]

[0194] Test Example 1 A toluene solution 1 with a solid content of 20% prepared in Production Example 1 and a silicone polymer 8 prepared in Production Example 8 were mixed to a solid content weight ratio of 3:1, and then diluted with toluene to prepare a treatment solution with a solid content of 1.5%. Polyester cloth (gray), nylon cloth (black), and cotton cloth (beige) were immersed in this treatment solution and then lightly dehydrated in a centrifugal dehydrator for about 10 seconds. The wet pickup was approximately 65% ​​(polyester cloth), approximately 40% (nylon cloth), and approximately 95% (cotton cloth). After drying these treated cloths overnight at room temperature, they were cured by passing them through a pin tenter at 170°C for 3 minutes. The water repellency of the test cloths treated in this way was evaluated using the water repellency test and strong water repellency test according to the spray method of JIS L-1092. The water repellency results are shown in Table 5.

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

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

[0197] Comparative Test Example 1 Toluene solution 1 with a solid content of 20%, prepared in Production Example 1, was further diluted with toluene to a solid content of 1.5%, and a water repellency test was performed on 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 2-7, prepared in Production Examples 2-7 with a solid content of 20%, was diluted with toluene (solid content of 1.5%) in the same manner as in Comparative Test Example 1, and a water repellency test was performed on the cloth in the same manner as in Test Example 1. The results are shown in Table 5.

[0199] Comparative Test Example 8 The silicone polymer 8 prepared in Production Example 8 was diluted with toluene (solids content concentration 1.5%), and a water repellency test was performed on a cloth in the same manner as in Test Example 1. The results are shown in Table 5.

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

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

[0202] Test Example 10 A 30% solids aqueous dispersion 11 prepared in Production Example 11 and a 30% solids aqueous dispersion 23 prepared in Production Example 23 were prepared in a weight ratio of 90:10 and further diluted with tap water to prepare a 1.5% solids treatment solution. Polyester cloth (gray), nylon cloth (black), and polyester cloth (white) were immersed in this treatment solution and then squeezed with a mangle. The wet pickup was approximately 55% (polyester cloth black), approximately 35% (nylon cloth), and approximately 65% ​​(polyester cloth white). These treated cloths were passed through a pin tenter at 170°C for 1 minute to dry and cure. The water repellency of the test cloths treated in this way was evaluated using the water repellency test and strong water repellency test according to the spray method of JIS L-1092. The water repellency results are shown in Table 6. Furthermore, Table 6 similarly shows the water repellency evaluation results of test fabrics that were washed 10 times and then dried in a tumble dryer (60°C for 30 minutes) in accordance with JIS L-0217 103. Furthermore, the white polyester fabric underwent a slip resistance test according to JIS-L-1096 Method B, while the gray polyester fabric underwent texture evaluation and chalk mark evaluation. The results are shown in Table 7.

[0203] Test examples 11-18, 24-26 Aqueous dispersions 12-22 with a solid content of 30% prepared in Production Examples 12-22 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 solution was prepared in the same manner as in Test Example 10. A water repellency test was performed by treating a cloth with this treatment solution in the same manner as in Test Example 6. The results are shown in Table 6.

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

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

[0206] Test Example 23 A 30% solids aqueous dispersion 18 prepared in Production Example 18 and a 30% solids aqueous dispersion 24 prepared in Production Example 24 were prepared in a weight ratio of 90:10, and a treatment solution was prepared in the same manner as in Test Example 10. A water repellency test was performed by treating a cloth with this treatment solution in the same manner as in Test Example 10. The results are shown in Table 6.

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

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

[0209] Comparative Test Example 11 A water dispersion 11 with a solid content of 30% prepared in Production Example 11 and a comparative water dispersion 7 with a solid content of 30% prepared in Comparative Production Example 7 were prepared in a weight ratio of 90:10. These were then diluted with tap water to a solid content of 1.5% to prepare a treatment solution. A water repellency test was performed using this treatment solution on a cloth in the same manner as in Test Example 10. The results are shown in Table 6.

[0210] Comparative study examples 12-19, 25-27 Aqueous dispersions with a solid content of 30% prepared in Production Examples 12-22 and comparative aqueous dispersion 7 with a solid content of 30% prepared in Comparative Production Example 7 were treated with a treatment solution in the same manner as in Comparative Test Example 7. A water repellency test was performed by treating a cloth with this treatment solution in the same manner as in Test Example 10. The results are shown in Table 6.

[0211] Comparative study examples 20, 28-30 The aqueous dispersions 14 and 21-23, each with a solid content of 30%, prepared in manufacturing examples 14 and 21-23, were diluted with tap water to a solid content of 1.5% to prepare a treatment solution. A water repellency test was performed using this treatment solution on a cloth in the same manner as in test example 10. The results are shown in Table 6.

[0212] Comparative Test Examples 21-24 A 30% solids aqueous dispersion 14 prepared in Production Example 14 and comparative 30% solids aqueous dispersions 6 and 8-10 prepared in Comparative Production Examples 6 and 8-10 were compared. A treatment solution was prepared in the same manner as in Test Example 11. A water repellency test was performed by treating a cloth with this treatment solution in the same manner as in Test Example 6. The results are shown in Table 6.

[0213] Comparative Test Example 31 A 30% solids aqueous dispersion 11 prepared in Production Example 11 was diluted with tap water to prepare a 1.5% solids treatment solution. A gray polyester cloth was immersed in this treatment solution and then wrung out with a mangle. The wet pickup rate was approximately 55%. This treated cloth was passed through a pin tenter at 170°C for 1 minute to dry and cure. Texture and chalk mark evaluations were performed using the test cloths treated in this way. The results are shown in Table 8.

[0214] Comparative Test Example 32 A 30% solids aqueous dispersion 12 prepared in Manufacturing Example 12 was diluted with tap water to prepare a 1.5% solids treatment solution. A gray polyester cloth was immersed in this treatment solution and then wrung out with a mangle. The wet pickup rate was approximately 55%. This treated cloth was passed through a pin tenter at 170°C for 1 minute to dry and cure. Texture and chalk mark evaluations were performed using the test cloths treated in this way. The results are shown in Table 8.

[0215] Slip resistance tests were conducted for test examples 13, 21, and 22, and comparative test examples 14, 20-24. 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, and 31-32, in addition to texture evaluation and chalk mark evaluation, gum-up evaluation and defoaming performance evaluation were performed on the treatment solution. 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 agents disclosed herein can be used, for example, as water-repellent and oil-repellent agents, antifouling agents, and dirt-removing agents.

Claims

1. (A) Repeating units derived from at least one water- and oil-repellent monomer selected from fluorine-containing monomers (A1) and non-fluorine monomers (A2) having hydrocarbon groups with 7 to 40 carbon atoms, in an amount of 40 to 100% by weight relative to the water- and oil-repellent polymer. A water- and oil-repellent polymer having a non-fluorine monomer (A2) of 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 between 1 and 3. A water-repellent and oil-repellent polymer that is a monomer represented by (excluding behenyl (meth)acrylate), (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 of these independently represents a hydrogen atom, a C1-C20 alkyl group, a C6-C20 aryl group, or a C1-C4 alkoxy group. R ５２ Each of these independently represents a saturated hydrocarbon group with 23 to 40 carbon atoms. R ５３ Each of these 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. R 51 and R 53 do not have an alkyl group having 3 to 22 carbon atoms or an unsaturated hydrocarbon group having 8 to 40 carbon atoms. 'a' represents an integer greater than or equal to 0, 'b' represents an integer greater than or equal to 1, and (a + b) is between 10 and 200. The silicone polymer shown, and (C) Liquid media A surface treatment agent comprising the above.

2. The water-repellent and oil-repellent monomer is a fluorine-containing monomer (A1), The fluorine-containing monomer (A1) is given by 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 These are directly bonded or divalent organic groups, Rf is a fluoroalkyl group having 1 to 20 carbon atoms. The surface treatment agent according to claim 1, which is a compound represented by .

3. In the fluorine-containing monomer (A1), X １１ Y is a hydrogen atom, a methyl group, or a chlorine atom. １１ is -O-, Z １１ The surface treatment agent according to claim 2, wherein is directly bonded 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 the fluorine-containing monomer (A1) has 1 to 6 carbon atoms in Rf.

5. 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 - (where m is an integer between 1 and 5) or -C ６ H ６ - (This is a phenylene group.) A surface treatment agent according to any one of claims 1 to 4.

6. The nonfluorine monomer (A2) is given by 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 This is a hydrocarbon group having 7 to 40 carbon atoms. The compound shown by, 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 This is a directly bonded, divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms. Z ２ Each of these is a divalent to tetravalent linking group having at least one group selected from direct bonds, -O-, and -NH-, R ２ These are, independently, hydrocarbon groups having 7 to 40 carbon atoms. p is either 1 or 2. The compound shown by, and formula: R ２２ -C(=O)-NH-R ２３ -O-R ２１ [In the formula, R ２１ This is an organic residue having an ethylenically unsaturated polymerizable group. R ２２ These are hydrocarbon groups with 7 to 40 carbon atoms. R ２３ This is a hydrocarbon group having 1 to 5 carbon atoms. The surface treatment agent according to any one of claims 1 to 5, which is at least one monomer selected from the group consisting of compounds represented by .

7. Fluorine-containing monomer (A1) 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 It is at least one compound selected from the group consisting of the following: The non-fluorine monomer (A2) Stearyl (meth)acrylate and behenyl (meth)acrylate, Palmitic acid amidoethyl acrylate and stearic acid amidoethyl acrylate, [In the above formula, m is an integer from 1 to 5, and n is an integer from 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, and 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.

8. The amount of the water- and oil-repellent polymer (A) is 0.1 to 60% by weight relative to the surface treatment agent. The surface treatment agent according to any one of claims 1 to 7, wherein the amount of silicone polymer (B) is 1 to 100 parts by weight per 100 parts by weight of water-repellent and oil-repellent polymer (A).

9. Water-repellent and oil-repellent polymers, (A3) Repeating units derived from nonfluorine-free, non-crosslinkable monomers, and (A4) Repeating units derived from non-fluorine crosslinkable monomers A surface treatment agent according to any one of claims 1 to 8, further comprising at least one selected from the group consisting of the above.

10. The nonfluorine, non-crosslinked 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 9, wherein the non-fluorine crosslinkable monomer (A4) is at least one compound selected from the group consisting of diacetone acrylamide, (meth)acrylamide, N-methylolacrylamide, 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.

11. In silicone polymers, R ５１ and R ５３ The surface treatment agent according to any one of claims 1 to 10, wherein the alkyl group has 3 to 22 carbon atoms.

12. In silicone polymers, R ５１ and R ５３ The surface treatment agent according to any one of claims 1 to 11, wherein each of them is independently a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms.

13. The amount of water- and oil-repellent monomer is 32 to 98% by weight relative to the water- and oil-repellent polymer (A). The amount of non-fluorine, non-crosslinked monomer (A3) is 2 to 68% by weight relative to the water-repellent and oil-repellent polymer. The surface treatment agent according to claim 9 or 10, wherein the amount of the non-fluorine crosslinkable monomer (A4) is 50 parts by weight or less per 100 parts by weight of the water-repellent and oil-repellent monomer.

14. The surface treatment agent according to any one of claims 1 to 13, wherein the surface treatment agent is a water-repellent or oil-repellent agent, an antifouling agent, or a dirt-removing agent.

15. (A) Repeating units derived from at least one water- and oil-repellent monomer selected from fluorine-containing monomers (A1) and non-fluorine monomers (A2) having hydrocarbon groups with 7 to 40 carbon atoms, in an amount of 40 to 100% by weight relative to the water- and oil-repellent polymer. A water- and oil-repellent polymer having a non-fluorine monomer (A2) of 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 between 1 and 3. An auxiliary agent used in a surface treatment agent containing a water- and oil-repellent polymer which is a monomer represented by (excluding behenyl (meth)acrylate), (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 of these independently represents a hydrogen atom, a C1-C20 alkyl group, a C6-C20 aryl group, or a C1-C4 alkoxy group. R ５２ Each of these independently represents a saturated hydrocarbon group with 23 to 40 carbon atoms. R ５３ Each of these 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. R 51 and R 53 do not have an alkyl group having 3 to 22 carbon atoms or an unsaturated hydrocarbon group having 8 to 40 carbon atoms. 'a' represents an integer greater than or equal to 0, 'b' represents an integer greater than or equal to 1, and (a + b) is between 10 and 200. An additive consisting of a silicone polymer as shown.

16. (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 of these independently represents a hydrogen atom, a C1-C20 alkyl group, a C6-C20 aryl group, or a C1-C4 alkoxy group. R ５２ Each of these independently represents a saturated hydrocarbon group with 23 to 40 carbon atoms. R ５３ Each of these 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. R 51 and R 53 do not have an alkyl group having 3 to 22 carbon atoms or an unsaturated hydrocarbon group having 8 to 40 carbon atoms. 'a' represents an integer greater than or equal to 0, 'b' represents an integer greater than or equal to 1, and (a + b) is between 10 and 200. The use of silicone polymers as additives, The auxiliary agent is a repeating unit derived from at least one water-repellent and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine monomer (A2) having a hydrocarbon group with 7 to 40 carbon atoms, in an amount of 40 to 100% by weight relative to (A) the water-repellent and oil-repellent polymer. A water- and oil-repellent polymer having a non-fluorine monomer (A2) of 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 between 1 and 3. Use in a surface treatment agent containing a water- and oil-repellent polymer which is a monomer represented by (excluding behenyl (meth)acrylate).

17. (i) A step of polymerizing a monomer containing at least one water- and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine monomer (A2) having a hydrocarbon group having 7 to 40 carbon atoms, in the presence of a liquid medium, to obtain an aqueous dispersion of a water- and oil-repellent polymer (A) having repeating units derived from the water- and oil-repellent monomer at a concentration of 40 to 100% by weight relative to the water- and oil-repellent polymer, and (ii) A step of adding a silicone polymer (B) to an aqueous dispersion of a water-repellent and oil-repellent polymer. A method for producing a surface treatment agent according to any one of claims 1 to 14, comprising the above.

18. A method for producing a treated substrate, comprising applying a surface treatment agent according to any one of claims 1 to 14 to the substrate.

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