Surface treatment agent

Abstract

The present invention is a surface treatment agent comprising (A) a fluoropolyether group-containing polymer and (B) a siloxane polymer, wherein the fluoropolyether group-containing polymer is of the following formula (1) or (2) A surface treatment agent is provided, wherein the copolymer represented by , and the number average molecular weight of the siloxane polymer is greater than 350 and less than 10,000.

Description

Technology Field

[0001] The present disclosure relates to a surface treatment agent comprising a fluoropolyether group-containing polymer and a siloxane polymer. Background Technology

[0002] It is known that certain types of fluorine-containing compounds can provide excellent water repellency, oil repellency, and antifouling properties when used for surface treatment of a substrate. Patent Document 1 discloses a composition comprising a fluorine-containing polymer and a silicon-containing polymer that can provide a surface treatment layer with excellent frictional durability. Prior art literature

[0003] Japanese Patent Publication No. 2014-198850 The problem to be solved

[0004] The composition described in the above-mentioned patent document 1 can impart functions such as water and oil repellency to the substrate, but it may not be sufficient to meet the increasingly high demand for surface slipperiness.

[0005] The present disclosure aims to provide a surface treatment agent comprising a fluorine-containing polymer and a silicon-containing polymer that imparts high surface slipperiness to a substrate in addition to water and oil repellency, and also has excellent solubility in solvents. means of solving the problem

[0006] The present disclosure includes the following aspects.

[0007] [1] A composition comprising (A) a fluoropolyether group-containing polymer and (B) a siloxane polymer, and

[0008] The above fluoropolyether group-containing polymer is the following formula (1) or (2):

[0009]

[0010] [During the meal:

[0011] R F1 silver, Rf 1 -RF -O q - and;

[0012] R F2 is, -Rf 2 p -R F -O q - and;

[0013] Rf 1 Silver, C which may be substituted by one or more fluorine atoms 1-16 It is an alkyl group;

[0014] Rf 2 C, which may be substituted by one or more fluorine atoms. 1-6 It is an alkylene group;

[0015] R F are, each independently, divalent fluoropolyether groups;

[0016] p is 0 or 1 and;

[0017] q is, each independently, 0 or 1 and;

[0018] R 4 is, independently in each appearance, R 4a or R 4b And;

[0019] R 4a is a divalent organic group having a bridging group, independently in each appearance;

[0020] R 4b is a divalent organic group that does not have a bridging group, independently in each appearance;

[0021] The above-mentioned crosslinking group is a group comprising a carbon-carbon double bond, a carbon-carbon triple bond, a cyclic ether group, a hydroxyl group, a thiol group, an amino group, an azide group, a nitrogen-containing heterocyclic group, an isocyanate group, a halogen atom, a phosphate-containing group, or a silane coupling group, or a precursor group thereof;

[0022] n is an integer from 1 to 100;

[0023] Xa are, each independently, divalent organic groups;

[0024] X b are, each independently, divalent organic groups;

[0025] R a are, respectively, alkyl, phenyl, -SR a1 , -OR a2 , -NR a3 2,

[0026]

[0027] And;

[0028] R a1 , R a2 , R a3 , R a4 , R a5 and R a6 Each is independently an alkyl group or a phenyl group;

[0029] R a7 It is a silver, hydrogen, or halogen atom.

[0030] It is a copolymer represented by,

[0031] A composition in which the number average molecular weight of the above siloxane polymer is greater than 350 and less than 10,000.

[0032] [2] R F is, each independently, formula:

[0033]

[0034] [In the middle of the meal, R Fa is, independently in each appearance, a hydrogen atom, a fluorine atom, or a chlorine atom, and

[0035] a, b, c, d, e, and f are each independently integers from 0 to 200, the sum of a, b, c, d, e, and f is 1 or greater, and the order of existence of each repetition unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the expression.

[0036] The composition described in [1] above, represented by the cause.

[0037] [3] R Fa The composition described in [2] above, which is a fluorine atom.

[0038] [4] R F are, respectively, the following expressions (f1), (f2), (f3), (f4) or (f5):

[0039]

[0040] [In the expression, d is an integer from 1 to 200, and e is 0 or 1.],

[0041]

[0042] [In the formula, c and d are each independently integers from 0 to 30;

[0043] e and f are, independently, integers from 1 to 200;

[0044] The sum of c, d, e, and f is an integer from 10 to 200;

[0045] The order of existence of each repetition unit enclosed in parentheses with the subscripts c, d, e, or f is arbitrary within the expression.

[0046]

[0047] [In the middle of the meal, R 6 It is OCF2 or OC2F4;

[0048] R 7 Silver, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It is a unit selected from, or a combination of two or three units selected from these units;

[0049] g is an integer from 2 to 100.

[0050]

[0051] [In the expression, e is an integer between 1 and 200 inclusive, a, b, c, d, and f are each independently integers between 0 and 200 inclusive, and the order of existence of each repetition unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the expression.]

[0052]

[0053] [In the expression, f is an integer between 1 and 200 inclusive, a, b, c, d, and e are each independently integers between 0 and 200 inclusive, and the order of existence of each repetition unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the expression.]

[0054] A composition described in any one of [1] to [3] above, which is represented by [1].

[0055] [5] R 4 is, R 4a A composition described in any one of [1] to [4] above.

[0056] [6] R 4a is, the following formula:

[0057]

[0058] [During the meal:

[0059] R 31 Silver, independently in each appearance, is a hydrogen atom or an alkyl group;

[0060] R 32 is an alkyl group that may be substituted by a hydrogen atom, a chlorine atom, a fluorine atom, or fluorine, independently in each appearance;

[0061] R 33 It is, independently in each appearance, a bridging group;

[0062] Y 1 silver, single bond, -C(=O)O-, -C(=O)NH-, -OC(=O)-, -NHC(=O)-, -O-, -N(R c)-, aromatic ring, aromatic ring having a substituent, or carbazolylene;

[0063] R c is, organic and,

[0064] Y 2 is a linker having 1 to 16 atoms in a single bond or main chain.

[0065] A composition described in any one of [1] to [5] above, which is represented by [1].

[0066] [7] The above-mentioned crosslinking group is an epoxy group, a glycidyl group, a dicyclic epoxy group, a vinyl group, an allyl group, an acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group, a vinyl ether group, a hydroxyl group, an oxetanyl group, an isocyanate group, a catechol group, a thiol group, an amino group, an alkylamino group, a dialkylamino group, an azide group, a phosphate-containing group, a carboxyl group, an imidazolyl group, a triazolyl group, a benzotriazolyl group, a tetrazolyl group, a halogen atom, or a silane coupling group, or a precursor group thereof, in the composition described in any one of [1] to [6].

[0067] [8] The above crosslinking group is an epoxy group, a glycidyl group, a cycloaliphatic epoxy group, an acryloyl group, or a methacryloyl group, a composition described in any one of [1] to [7].

[0068] [9] n is an integer from 2 to 50, a composition described in any one of [1] to [8] above.

[0069]

[10] The above siloxane polymer is of the following formula:

[0070]

[0071] [During the meal:

[0072] R 21 Silver, independently in each appearance, hydrogen atom, C 1-6 It is an alkyl group or an aryl group, and

[0073] R 22is, independently in each appearance, a hydrogen atom, C 1-6 It is an alkyl group or an aryl group, and

[0074] R 23 Silver, hydrogen atom, C 1-6 It is an alkyl group or an aryl group, and

[0075] R 24 is, hydrogen atom, C 1-6 It is an alkyl group or an aryl group, and

[0076] R 25 is a hydrogen atom or a monovalent organic group, and

[0077] R 26 It is silver, a hydrogen atom, or a monovalent organic group, and

[0078] p is an arbitrary integer.

[0079] A composition described in any one of [1] to [9] above, which is a siloxane polymer represented by

[0080]

[11] R 25 and R 26 silver, C 1-6 The composition described in

[10] above, which is an alkyl group.

[0081]

[12] R 25 is C 1-6 It is an alkyl group, and

[0082] R 26 silver, -R 27 -R 28 And,

[0083] R 27 It is silver, a divalent organic group, an oxygen atom, or a single bond, and

[0084] R 28 Silver, hydrogen atom, -OH, -CO-CH=CH2, -CO-C(CH3)=CH2, epoxy group, alicyclic epoxy group, amino group, carboxyl group, vinyl group, alkoxy group, or thiol group,

[0085] The composition described in

[10] above.

[0086]

[13] R 25 and R 26silver, -R 27 -R 28 And,

[0087] R 27 It is silver, a divalent organic group, an oxygen atom, or a single bond, and

[0088] R 28 Silver, hydrogen atom, -OH, -CO-CH=CH2, -CO-C(CH3)=CH2, epoxy group, alicyclic epoxy group, amino group, carboxyl group, vinyl group, alkoxy group, or thiol group,

[0089] The composition described in

[10] above.

[0090]

[14] A composition described in any one of [1] to

[13] , wherein the number average molecular weight of the siloxane polymer is 800 to 8,000.

[0091]

[15] A composition described in any one of [1] to

[14] , wherein the content of the above siloxane polymer is 1 to 300 parts by mass per 100 parts by mass of the above fluoropolyether group-containing polymer.

[0092]

[16] A surface treatment agent comprising a composition described in any one of [1] to

[15] above.

[0093]

[17] A composition described in any one of [1] to

[15] above, a surface treatment agent described in

[16] above; and

[0094] Composition forming a matrix

[0095] A curable composition comprising

[0096]

[18] The composition forming the matrix above is an acrylic resin or an epoxy resin, a curable composition as described in

[17] .

[0097]

[19] A film formed by the composition described in any one of [1] to

[15] above, the surface treatment agent described in

[16] above, and / or the curable composition described in

[17] or

[18] above.

[0098]

[20] An article comprising a substrate and a layer formed on the surface of the substrate by the composition described in any one of claims [1] to

[15] , the surface treatment agent described in

[16] , and / or the curable composition described in

[17] or

[18] .

[0099]

[21] The above article is an optical component, the article described in

[20] above.

[0100]

[22] The article described in

[20] above, which is a LiDAR cover member.

[0101]

[23] The item described in

[20] above, which is a sensor component.

[0102]

[24] The instrument panel cover member, the article described in

[20] above.

[0103]

[25] An automobile interior component, the item described in

[20] above. Effects of the invention

[0104] The surface treatment agent of the present disclosure imparts high surface slipperiness in addition to water and oil repellency to the base and also has excellent solubility in solvents. Specific details for implementing the invention

[0105] As used in this specification, "monovalent organic group" means a monovalent group containing carbon. Unless otherwise specifically stated, a monovalent organic group may be a hydrocarbon group or a derivative thereof. A derivative of a hydrocarbon group means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc., at the end of the hydrocarbon group or in the molecular chain. Also, when simply referred to as "organic group," it means a monovalent organic group. Furthermore, "divalent organic group" means a divalent group containing carbon. Such a divalent organic group is not particularly limited, but may include a divalent group from which one hydrogen atom has also been removed from the organic group.

[0106] As used herein, the term "hydrocarbon group" means a group comprising carbon and hydrogen, from which one hydrogen atom has been removed from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but may be substituted by one or more substituents, such as C 1-20 Hydrocarbon groups, for example, aliphatic hydrocarbon groups, aromatic hydrocarbon groups, etc. The above “aliphatic hydrocarbon group” may be straight-chain, branched-chain, or cyclic, and may be saturated or unsaturated. In addition, the hydrocarbon group may include one or more cyclic structures.

[0107] When used in this specification, the substituent of the “hydrocarbon group” is not particularly limited, but may be, for example, a halogen atom, or may be substituted by one or more halogen atoms, C 1-6 Alkyl group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 Cycloalkyl group, C 3-10 Unsaturated cycloalkyl group, 5 to 10-membered heterocyclyl group, 5 to 10-membered unsaturated heterocyclyl group, C 6-10 One or more groups selected from an aryl group and a heteroaryl group of 5 to 10 can be included.

[0108] [Composition]

[0109] The composition of the present disclosure will be described below.

[0110] The composition of the present disclosure comprises (A) a fluoropolyether group-containing polymer and (B) a siloxane polymer.

[0111] [(A) Fluoropolyether group-containing polymer]

[0112] The above fluoropolyether group-containing polymer is the following formula (1) or (2):

[0113]

[0114] [During the meal:

[0115] R F1 silver, Rf 1 -R F -O q - and;

[0116] R F2 is, -Rf 2 p -R F -O q - and;

[0117] Rf 1 Silver, C which may be substituted by one or more fluorine atoms 1-16 It is an alkyl group;

[0118] Rf 2 C, which may be substituted by one or more fluorine atoms. 1-6 It is an alkylene group;

[0119] R F are, each independently, divalent fluoropolyether groups;

[0120] p is 0 or 1 and;

[0121] q is, each independently, 0 or 1 and;

[0122] R 4 is, independently in each appearance, R 4a or R 4b And;

[0123] R 4a is a divalent organic group having a bridging group, independently in each appearance;

[0124] R 4b is a divalent organic group that does not have a bridging group, independently in each appearance;

[0125] The above-mentioned crosslinking group is a group comprising a carbon-carbon double bond, a carbon-carbon triple bond, a cyclic ether group, a hydroxyl group, a thiol group, an amino group, an azide group, a nitrogen-containing heterocyclic group, an isocyanate group, a halogen atom, a phosphate-containing group, or a silane coupling group, or a precursor group thereof;

[0126] n is an integer from 1 to 100;

[0127] X a are, each independently, divalent organic groups;

[0128] X b are, each independently, divalent organic groups;

[0129] R a are, respectively, alkyl, phenyl, -SR a1 , -OR a2 , -NR a3 2,

[0130]

[0131] And;

[0132] R a1 , R a2 , R a3 , R a4 , R a5 and R a6 Each is independently an alkyl group or a phenyl group;

[0133] R a7 It is a silver, hydrogen, or halogen atom.

[0134] It is a copolymer represented as.

[0135] In the above equation (1), R F1 silver, Rf 1 -R F -O q -am.

[0136] In the above equation (2), R F2 is, -Rf 2 p -R F -O q -am.

[0137] In the above equation, Rf 1 C, which may each independently be substituted by one or more fluorine atoms 1-16 It is an alkyl group.

[0138] C which may be substituted by one or more of the above-mentioned fluorine atoms1-16 "C" in the alkyl group 1-16 The alkyl group may be a straight chain or a branched chain, and preferably a straight or branched C 1-6 Alkyl groups, especially C 1-3 It is an alkyl group, and more preferably a straight-chain C 1-6 Alkyl groups, especially straight-chain C 1-3 It is an alkyl group.

[0139] The above Rf 1 C, preferably substituted by one or more fluorine atoms. 1-16 It is an alkyl group, more preferably CF2H-C 1-15 It is a perfluoroalkylene group, and more preferably C 1-16 It is a perfluoroalkyl group.

[0140] The above C 1-16 The perfluoroalkyl group may be straight or branched, and preferably a straight or branched C 1-6 Perfluoroalkyl groups, especially C 1-3 It is a perfluoroalkyl group, and more preferably a straight-chain C 1-6 Perfluoroalkyl groups, especially C 1-3 It is a perfluoroalkyl group, specifically -CF3, -CF2CF3, or -CF2CF2CF3.

[0141] In the above equation, Rf 2 C, which may be substituted by one or more fluorine atoms. 1-6 It is an alkylene group.

[0142] C which may be substituted by one or more of the above-mentioned fluorine atoms 1-6 "C" in the alkylene group 1-6 The "alkylene group" may be a straight chain or a branched chain, and preferably a straight or branched C 1-3 It is an alkylene group, and more preferably a straight-chain C 1-3 It is an alkylene group.

[0143] The above Rf 2 C, preferably substituted by one or more fluorine atoms1-6 It is an alkylene group, and more preferably C 1-6 It is a perfluoroalkylene group, and more preferably C 1-3 It is a perfluoroalkylene group.

[0144] The above C 1-6 The perfluoroalkylene group may be a straight chain or a branched chain, and preferably a straight or branched C 1-3 It is a perfluoroalkylene group, and more preferably a straight-chain C 1-3 It is a perfluoroalkyl group, specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0145] In the above formula, p is 0 or 1. In one mode, p is 0. In another mode, p is 1.

[0146] In the above equation, q is, independently, 0 or 1. In one mode, q is 0. In another mode, q is 1.

[0147] In the above equations (1) and (2), R F Each is independently a divalent fluoropolyether group.

[0148] R F is, preferably formula:

[0149]

[0150] [During the meal:

[0151] R Fa is, independently in each appearance, a hydrogen atom, a fluorine atom, or a chlorine atom, and

[0152] a, b, c, d, e, and f are each independently integers from 0 to 200, and the sum of a, b, c, d, e, and f is 1 or greater. The order of existence of each repetition unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary within the expression.

[0153] It is a device indicated as.

[0154] R Fa is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom.

[0155] a, b, c, d, e, and f may, preferably, each independently be integers from 0 to 100.

[0156] The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. The sum of a, b, c, d, e, and f is preferably 200 or less, more preferably 100 or less, even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0157] These repeating units may be linear or branched. For example, the above repeating unit is -(OC6F 12 )- is, -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))- etc. 10 )- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))- etc. -(OC4F8)- may be -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OCF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)- and -(OCF2CF(C2F5))-. -(OC3F6)-(i.e., among the above formulas, R Fa(is a fluorine atom) may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)- and -(OCF2CF(CF3))-. -(OC2F4)- may be any of -(OCF2CF2)- and -(OCF(CF3))-.

[0158] In one embodiment, the repeating unit is in a linear form. By making the repeating unit in a linear form, the surface slipperiness, frictional durability, etc. of the surface treatment layer can be improved.

[0159] In one embodiment, the repeating unit is branched. By making the repeating unit branched, the kinetic friction coefficient of the surface treatment layer can be increased.

[0160] In one mode, R F is a group that is independently represented by any of the following formulas (f1) to (f5).

[0161]

[0162] [In the expression, d is an integer from 1 to 200, and e is 0 or 1.];

[0163]

[0164] [In the expression, c and d are each independently integers from 0 to 30, and e and f are each independently integers from 1 to 200, and

[0165] The sum of c, d, e, and f is 2 or greater, and

[0166] The order of existence of each repetition unit enclosed in parentheses with the subscripts c, d, e, or f is arbitrary within the expression.

[0167]

[0168] [In the middle of the meal, R 6 is OCF2 or OC2F4, and

[0169] R 7OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It is a unit selected from, or a combination of two or three units independently selected from these units, and

[0170] g is an integer from 2 to 100.

[0171]

[0172] [In the expression, e is an integer between 1 and 200 inclusive, a, b, c, d, and f are each independently integers between 0 and 200 inclusive, the sum of a, b, c, d, e, and f is at least 1, and the order of existence of each repetition unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the expression.]

[0173]

[0174] [In the expression, f is an integer between 1 and 200 inclusive, a, b, c, d, and e are each independently integers between 0 and 200 inclusive, the sum of a, b, c, d, e, and f is at least 1, and the order of existence of each repetition unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the expression.]

[0175] In the above formula (f1), d is preferably an integer from 5 to 200, more preferably from 10 to 100, even more preferably from 15 to 50, e.g. from 25 to 35. In one embodiment, e is 0. In another embodiment, e is 1. The above formula (f1) is preferably -(OCF2CF2CF2) d -(OCF2CF2) e - or -(OCF(CF3)CF2) d -(OCF(CF3)) e It is a group indicated by -, and more preferably, -(OCF2CF2CF2) d -(OCF2CF2) eIt is a device indicated by -.

[0176] In the above formula (f2), e and f are each independently integers, preferably 5 or more and 200 or less, more preferably 10 to 200. Additionally, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f It is a term denoted by -. In another mode, Equation (f2) is -(OC2F4) e -(OCF2) f Contribution is also indicated by -

[0177] In the above equation (f3), R 6 It is preferably OC2F4. In the above (f3), R 7The group is preferably selected from OC2F4, OC3F6, and OC4F8, or a combination of two or three groups independently selected from these groups, and more preferably, a group selected from OC3F6 and OC4F8. As combinations of two or three groups independently selected from OC2F4, OC3F6, and OC4F8, are not particularly limited, but include, for example -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, Examples include -OC3F6OC3F6OC2F4- and -OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It may be either a straight chain or a branched chain, and preferably a straight chain. In this embodiment, the formula (f3) is preferably -(OC2F4-OC3F6) g - or -(OC2F4-OC4F8) g -am.

[0178] In the above formula (f4), e is preferably an integer of 1 or more and 100 or less, more preferably of 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0179] In the above formula (f5), f is preferably an integer of 1 or more and 100 or less, more preferably of 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0180] In one embodiment, the above R F is the basis represented by the above equation (f1).

[0181] In one embodiment, the above R F is a unit represented by the above equation (f2).

[0182] In one embodiment, the above R F is the basis represented by the above equation (f3).

[0183] In one embodiment, the above R F is the basis represented by the above equation (f4).

[0184] In one embodiment, the above R F is the basis represented by the above equation (f5).

[0185] The above R F In this case, the ratio of e to f (hereinafter referred to as the “e / f ratio”) is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By making the e / f ratio 10 or less, the slipperiness, frictional durability, and chemical resistance (e.g., durability against artificial sweat) of the surface treatment layer obtained from this compound are further improved. The smaller the e / f ratio, the more the slipperiness and frictional durability of the surface treatment layer are improved. Meanwhile, by making the e / f ratio 0.1 or more, the stability of the compound can be further increased. The larger the e / f ratio, the more the stability of the compound is improved.

[0186] In one embodiment, the e / f ratio is preferably 0.2 to 0.95, and more preferably 0.2 to 0.9.

[0187] In one embodiment, with respect to heat resistance, the e / f ratio is preferably 1.0 or higher, and more preferably 1.0 to 2.0.

[0188] In the above fluoropolyether group-containing compound, R F1 and R F2 The number average molecular weight of the fraction is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000. In this specification, R F1 and R F2 The number average molecular weight of is 19 It is defined as the value measured by F-NMR.

[0189] In another aspect, R F1 and R F2 The number average molecular weight of the portion may be 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 2,000 to 10,000, for example 3,000 to 6,000.

[0190] In another aspect, R F1 and R F2 The number average molecular weight of the portion may be 4,000 to 30,000, preferably 5,000 to 10,000, more preferably 6,000 to 10,000.

[0191] In the above formula, R 4 is, independently in each appearance, R 4a or R 4b am.

[0192] The above R 4a is a divalent organic group having a bridging group independently in each appearance.

[0193] The above-mentioned crosslinking group refers to a group capable of forming a crosslinked structure by causing a reaction under specific conditions.

[0194] The above-mentioned crosslinking group is preferably a group comprising a carbon-carbon double bond, a carbon-carbon triple bond, a cyclic ether group, a hydroxyl group, a thiol group, an amino group, an azide group, a nitrogen-containing heterocyclic group, an isocyanate group, a halogen atom, a phosphate-containing group, or a silane coupling group, or a precursor group thereof.

[0195] Examples of the above-mentioned crosslinking groups include, for instance, epoxy groups, glycidyl groups, alicyclic epoxy groups, vinyl groups, allyl groups, acryloyl groups, cinnamoyl groups, 2,4-hexadienoyl groups, vinyl ether (vinyloxy) groups, hydroxyl groups, oxetanyl groups, isocyanate groups, catechol groups, thiol groups, amino groups, alkylamino groups, dialkylamino groups, azide groups, phosphate-containing groups, carboxyl groups, imidazolyl groups, triazolyl groups, benzotriazolyl groups, tetrazolyl groups, halogen atoms, or silane coupling groups, or precursor groups thereof.

[0196] The above-mentioned cycloaliphatic epoxy group is preferably of the following formula:

[0197]

[0198] (In the expression, n is an integer from 1 to 5.)

[0199] It is a device indicated as.

[0200] The above-mentioned cycloaliphatic epoxy group is more preferably

[0201]

[0202] am.

[0203] The acrylyl group that may be substituted above is CH2=CX 1 It is a unit represented by -C(O)-.

[0204] The above X 1It represents an alkyl group having 1 to 10 carbon atoms that may be substituted with silver, hydrogen atoms, chlorine atoms, fluorine atoms, or fluorine, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, for example, a methyl group.

[0205] The above-mentioned acryloyl group that may be substituted is preferably an acryloyl group or a methacryloyl group. Hereinafter, the acryloyl group and the methacryloyl group are collectively referred to as "(meth)acryloyl group."

[0206] The above phosphoric acid-containing group is not particularly limited as long as it contains a phosphoric acid group, for example, C 1-6 Alkylene-OP(O)(OH)(OR)(wherein R is a hydrogen atom or C 1-3 It can be an alkyl.)

[0207] In one embodiment, the crosslinking group may be an epoxy group, a glycidyl group, a dicyclic epoxy group, a vinyl group, an allyl group, a (meth)acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group, or a vinyl ether (vinyloxy) group.

[0208] In a preferred embodiment, the crosslinking group is an epoxy group, a glycidyl group, or CH2=CX 1' -C(O)-(formula, X 1' ...is represented by a carbon 1 to 10 alkyl group that may be substituted by a hydrogen atom, a chlorine atom, a fluorine atom, or fluorine, and preferably may be an epoxy group, a glycidyl group, or a (meth)acryloyl group.

[0209] In another preferred embodiment, the crosslinking group may be an epoxy group, a glycidyl group, a dicyclic epoxy group, or a (meth)acryloyl group, preferably an epoxy group, a glycidyl group, or a dicyclic epoxy group, more preferably an epoxy group or a glycidyl group.

[0210] In a preferred embodiment, R 4a is, the following formula:

[0211]

[0212] [During the meal:

[0213] R 31 In each appearance, independently, is a hydrogen atom or an alkyl group;

[0214] R 32 is, in each appearance, an alkyl group that may be independently substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or fluorine;

[0215] R 33 ...is, in each appearance, independently, a bridging group;

[0216] Y 1 silver, single bond, -C(=O)O-, -C(=O)NH-, -OC(=O)-, -NHC(=O)-, -O-, -N(R c )-, aromatic ring, aromatic ring having a substituent, or carbazolylene;

[0217] R c is, organic and,

[0218] Y 2 is a linker having 1 to 16 atoms in a single bond or main chain.

[0219] It is a device indicated as.

[0220] Among the above formulas, R 31 In each appearance, silver independently represents a hydrogen atom or an alkyl group. The alkyl group is preferably C 1-6 Alkyl group, more preferably C 1-3 It is an alkyl group, more preferably a methyl group or an ethyl group. R 31 It is preferably a hydrogen atom.

[0221] Among the above formulas, R 32 represents, in each appearance, an alkyl group that may be independently substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or fluorine. The alkyl group is preferably C 1-6Alkyl group, more preferably C 1-3 It is an alkyl group, more preferably a methyl group or an ethyl group. R 32 is preferably a methyl group or a hydrogen atom, and more preferably a hydrogen atom.

[0222] The above R 33 In each appearance, it is a bridging group independently. The bridging group has the same meaning as above.

[0223] In a preferred embodiment, R 33 It may be an epoxy group, a glycidyl group, alicyclic epoxy group, vinyl group, allyl group, an acryloyl group that may be substituted, a cinnamoyl group, a 2,4-hexadienoyl group, a vinyl ether (vinyloxy) group, a hydroxyl group, an oxetanyl group, an isocyanate group, a catechol group, a thiol group, an amino group, an alkylamino group, a dialkylamino group, an azide group, a phosphate-containing group, a carboxyl group, an imidazolyl group, a triazolyl group, a benzotriazolyl group, a tetrazolyl group, a halogen atom, or a silane coupling group, or a precursor group thereof.

[0224] In a more desirable embodiment, R 33 It may be an epoxy group, a glycidyl group, a dicyclic epoxy group, a vinyl group, an allyl group, a (meth)acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group, or a vinyl ether (vinyloxy) group.

[0225] In a more preferred embodiment, the crosslinking group may be an epoxy group, a glycidyl group, a dicyclic epoxy group, or a (meth)acryloyl group, preferably an epoxy group, a glycidyl group, or a (meth)acryloyl group.

[0226] Among the above formulas, Y 1 silver, single bond, -C(=O)O-, -C(=O)NH-, -OC(=O)-, -NHC(=O)-, -O-, -N(R c )-, is phenylene or carbazolylene. Here, R c represents an organic group, preferably an alkyl group. The alkyl group is preferably C 1-6Alkyl group, more preferably C 1-3 It is an alkyl group, more preferably a methyl group or an ethyl group. Y 1 These groups regarding , the left side is coupled to C in the equation, and the right side is Y 2 Combines with.

[0227] In one mode, Y 1 Silver, -C(=O)O-, -C(=O)NH-, -OC(=O)-, -NHC(=O)-, -O-, -N(R c )-, is phenylene or carbazolylene. Here, R c represents an organic group, preferably an alkyl group.

[0228] Y 1 It is preferably -C(=O)O-, -O-, or carbazolylene, more preferably -C(=O)O- or -O-, and even more preferably -C(=O)O-.

[0229] Among the above formulas, Y 2 represents a linker having 1 to 16 atoms of single bonds or a main chain, preferably 2 to 12, more preferably 2 to 10. Herein, the main chain refers to Y 2 Middle, Y 1 and R 33 It refers to the part that connects with the minimum number of atoms.

[0230] Y 2 As for, it is not specifically limited, but for example,

[0231] -(CH2-CH2-O) p1 -(p1 represents an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4),

[0232] -(CHR d ) p2-O-(p2 is an integer from 1 to 40, preferably an integer from 1 to 10, more preferably an integer from 1 to 6, even more preferably an integer from 1 to 4, and even more preferably an integer from 2 to 4, and R d is represented by hydrogen, or a methyl group),

[0233] -(CH2) p3 -O-(CH2) p4 -(p3 is an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4, and p4 is an integer from 0 to 10, preferably an integer from 0 to 6, more preferably an integer from 0 to 4, and in one embodiment, represents an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4),

[0234] -(CH2-CH2-O) p5 -CO-NH-CH2-CH2-O-(p5 represents an integer from 1 to 10),

[0235] -(CH2) p6 -(p6 represents an integer from 1 to 6),

[0236] -(CH2) p7 -O-CONH-(CH2) p8 -(p7 represents an integer from 1 to 8, preferably 2 or 4, and p8 represents an integer from 1 to 6, preferably 3),

[0237] -(CH2) p9 -NHC(=O)O-(CH2) p10 -(p9 represents an integer from 1 to 6, preferably 3, and p10 represents an integer from 1 to 8, preferably 2 or 4), or

[0238] -O-(but, Y 1 One example is (not -O-).

[0239] Desirable Y 2 As, -(CH2-CH2-O) p1-(p1 represents an integer from 1 to 10), -(CHR d ) p2 -O-(p2 is an integer from 1 to 40, and R d -(CH2) represents hydrogen, or a methyl group p3 -O-(CH2) p4 -(p3 is an integer from 1 to 10, and p4 represents an integer from 1 to 10) or -(CH2) p7 -O-CONH-(CH2) p8 -(p7 represents an integer from 1 to 8, preferably 2 or 4, and p8 represents an integer from 1 to 6, preferably 3). In addition, these groups have a left end on the molecular main chain side (Y 1 It binds to the side) and the right end is the functional group side (R) selected from substituent group A. 33 Combines to the side.

[0240] R 4a is, more preferably, the following formula:

[0241]

[0242] (during food, R 33 ...is the same meaning as above, and q2 is an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4, and even more preferably an integer from 2 to 4, and q3 is an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4, and even more preferably an integer from 1 to 2.)

[0243] It is a device indicated as.

[0244] The above R 4b is a divalent organic group that does not have a bridging group, independently in each appearance.

[0245] R 4b is, preferably -CHR 4c -CR 4d R 4e -is. Here, R 4cand R 4d Each independently represents a hydrogen atom or an alkyl group, and R 4e ging, -Y 3 -R 4f It is. Here, Y 3 The above Y 1 It has the same meaning as, and R 4f is an organic group that does not have a bridging group, and the later group R 4g via a linker, or directly Y 3 It is a group that binds to. That is, R 4f is, -linker-R 4g , or -R 4g am.

[0246] The linker in question is preferably,

[0247] (a) -(CH2-CH2-O) s1 -(s1 represents an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4.),

[0248] (b) -(CHR 4h ) s2 -O-(s2 represents a number of repetitions that is an integer from 1 to 40, preferably an integer from 1 to 10, more preferably an integer from 1 to 6, even more preferably an integer from 1 to 4, and even more preferably an integer from 2 to 4. R 4h represents a hydrogen or methyl group.),

[0249] (c) -(CH2) s3 -O-(CH2) s4 -(s3 is an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4, and s4 is an integer from 0 to 10, preferably an integer from 0 to 6, more preferably an integer from 0 to 4, and in one embodiment, represents an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4.),

[0250] (d) -(CH2-CH2-O) s1 -CO-NH-CH2-CH2-O-(s1 has the same meaning as above.),

[0251] (e) -(CH2) s5 -(s5 represents an integer from 1 to 6), or

[0252] (f) -(CH2) s6 -O-CONH-(CH2) s7 -(s6 represents an integer from 1 to 8, preferably 2 or 4. s7 represents an integer from 1 to 6, preferably 3.), or

[0253] (g) -O-(where Y 3 (It is not -O-)

[0254] am.

[0255] R 4g is, preferably, the following.

[0256] (i) alkyl group

[0257] Examples: Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, tert-butyl, Pentyl, Hexyl, Heptyl, Octyl, Dodecyl, Octadecyl

[0258] (ii) chain group containing a fluorine-substituted alkyl group

[0259] yes:

[0260]

[0261] (iii) a device comprising one or more ring portions selected from the group consisting of a monocyclic carbon ring, a bicyclic carbon ring, a tricyclic carbon ring, and a tetracyclic carbon ring.

[0262] yes:

[0263]

[0264] (iv) Hydrogen (provided that the hydrogen atom does not bond with the oxygen atom of the linker)

[0265] (v) a group containing imidazolium salt

[0266] yes:

[0267]

[0268] (vi) silicon-containing organisms

[0269]

[0270] Among the above formulas, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 Each independently represents an alkyl group or an aryl group.

[0271] The above alkyl group is not particularly limited, but may include an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and specifically, R 11 Regarding , it is an n-butyl group with a number of carbon atoms, and R 12 to R 17 Regarding it, it is a methyl group.

[0272] The above aryl group is not particularly limited, but may include an aryl group having 6 to 20 carbon atoms. The aryl group may include two or more rings. A preferred aryl group is a phenyl group.

[0273] The above alkyl and aryl groups may, if desired, contain heteroatoms, for example, nitrogen atoms, oxygen atoms, or sulfur atoms in their molecular chains or rings.

[0274] In addition, the above alkyl group and aryl group may, if desired, be substituted with a halogen; C, which may be substituted with one or more halogens. 1-6 Alkyl group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 Cycloalkyl group, C 3-10 Unsaturated cycloalkyl group, 5 to 10-membered heterocyclyl group, 5 to 10-membered unsaturated heterocyclyl group, C6-10 It may be substituted by one or more substituents selected from an aryl group and a heteroaryl group of 5 to 10 members.

[0275] Among the above formulas, R 18 Silver represents a divalent organic group.

[0276] The above R 18 silver, preferably -(CH2) r" -(wherein r" is an integer between 1 and 20, preferably an integer between 1 and 10), and more preferably, -(CH2) r" -(In the expression, r" is an integer between 1 and 10 inclusive).

[0277] In the above formula, n4 is, independently, an integer of 1 or more and 500 or less. The n4 is preferably 1 or more and 200 or less, more preferably 10 or more and 200 or less.

[0278] R 4g is, more preferably, a hydrogen atom (except for bonding to O to form a hydroxyl group), or an alkyl group that may be fluorinated and may also be bonded through an ethylene chain or an oxyethylene chain, and more preferably, a hydrogen atom, a methoxyethyl group, an isobutyl group, or R 4i -CF2-(CF2) s6 -(CH2) s7 -O-(CH2)2-(R 4i is a fluorine atom or a hydrogen atom, s6 is an integer from 0 to 6, and s7 is an integer from 1 to 6), and more preferably, is a 3-(perfluoroethyl)propoxyethyl group [formula: CF3-(CF2)-(CH2)3-O-(CH2)2-].

[0279] The above R 4 Among, constituent unit R 4a and constituent unit R 4b Each of them may form a block, or they may be randomly combined.

[0280] In one mode, R4 Among, constituent unit R 4a and constituent unit R 4b Each forms a block.

[0281] In one mode, R 4 Among, constituent unit R 4a and constituent unit R 4b ...combines randomly.

[0282] In one mode, R 4 is, R 4a is. That is, R 4 is a constituent unit R having a crosslinking group. 4a It consists of.

[0283] In a preferred embodiment, R 4a The number (degree of polymerization) is 1 to 100, preferably 2 to 70, more preferably 2 to 50, even more preferably 3 to 30, even more preferably 3 to 20, and particularly preferably 5 to 10.

[0284] In one mode, R 4 is, R 4b is. That is, R 4 is a constituent unit R that does not have a bridging group. 4b It consists of.

[0285] In a preferred embodiment, R 4b The number (degree of polymerization) is 1 to 100, preferably 2 to 70, more preferably 2 to 50, even more preferably 3 to 30, more preferably 3 to 20, and particularly preferably 5 to 10.

[0286] In the above formula, n is an integer from 1 to 100, preferably an integer from 2 to 70, more preferably an integer from 2 to 50, even more preferably an integer from 3 to 30, even more preferably an integer from 3 to 20, and particularly preferably an integer from 5 to 10.

[0287] In the above equations (1) and (2), X a Each is independently a divalent organic group.

[0288] In the above equations (1) and (2), X b Each is independently a divalent organic group.

[0289] Among the above formulas, -X a -X b - is a fluoropolyether group-containing polymer represented by formulas (1) and (2), wherein R F1 or R F2 Wow, R 4 It is interpreted as part of the linker connecting. Therefore, X a and X b If the compound represented by formulas (1) and (2) can exist stably, it can be any divalent organic contribution.

[0290] In one mode, X a is, each independently, the following formula:

[0291]

[0292] It is a unit represented as. In the expression, e, f, and g are each independently integers from 0 to 10, the sum of e, f, and g is 1 or greater, and the order of existence of each repeating unit enclosed in parentheses is arbitrary within the expression. Furthermore, the above unit is R on the left side F1 or R F2 Uh, the right side is X b Combines with.

[0293] In the above formula, Q is, in each appearance, independently an oxygen atom, phenylene, carbazolylene, -NR q -( Food, R q1 Q is an oxygen atom or an organic group (representing a hydrogen atom or an organic group) or a divalent polar group. Preferably, Q is an oxygen atom or a divalent polar group.

[0294] The "divalent polar group" in the above Q is not particularly limited, but includes -C(O)-, -C(=NR b )-, and -C(O)NR q2 -(Among these expressions, R q2 Examples include a hydrogen atom or a lower alkyl group. The “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, or n-propyl, and these may be substituted by one or more fluorine atoms.

[0295] In the above formula, Z is, in each appearance, independently a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group, preferably a fluorine atom. The “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, and even more preferably a trifluoromethyl group.

[0296] X a is, preferably, the following formula:

[0297]

[0298] [In the expression, e, f, and g have the same meaning as above, and the order of existence of each repetition unit enclosed in parentheses is arbitrary within the expression.]

[0299] It is a device represented as . In addition, these devices have a left end that is R F1 or R F2 Uh, the right side is X b Combines with.

[0300] In one mode, X a Is,

[0301]

[0302] [During the meal,

[0303] e1 is 0 or 1, and

[0304] f2, g2, and g3 are each independently integers from 1 to 10, and

[0305] g4 is 0 or 1.

[0306] It may be a period indicated by . These periods have a left end R F1 or R F2 Uh, the right side is X b Combines with.

[0307] In a preferred embodiment, X a Is,

[0308]

[0309] [In the formula, g2 is an integer from 1 to 10.]

[0310] It may be a period indicated by . These periods have a left end R F1 or R F2 Uh, the right side is X b Combines with.

[0311] Among the above formulas, X b Each is independently a divalent organic group.

[0312] In one mode, X b is, the following formula:

[0313]

[0314] [During the meal:

[0315] R b1 and R b2 are, each independently, hydrogen atoms, C 1-3 It is an alkyl group, a phenyl group, or -CN, and

[0316] R b3 C, which may be single-bonded or substituted 1-6 It is an alkylene group.

[0317] It may be a period indicated as. In addition, such a period has an X on the left side. a Uh, the right side is R 4 Combines with.

[0318] The above R b1 and Rb2 are, each independently, preferably C 1-3 It is an alkyl group, a phenyl group, or -CN, and more preferably, C 1-3 It is an alkyl group or -CN. C 1-3 The alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0319] In one mode, R b1 silver, C 1-3 It is an alkyl group, preferably a methyl group, and R b2 is a hydrogen atom or -CN.

[0320] The above R b3 In the case of "C that may be substituted" 1-6 The substituent in the "alkylene group" is preferably C 1-3 It is an alkyl group or a phenyl group, preferably C 1-3 It is an alkyl group. C 1-3 The alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group. The corresponding substituent may be one or two or more.

[0321] The above R b3 C in 1-6 The alkylene group is preferably C 1-3 An alkylene group, more preferably C 2-3 It can be an alkylene group, for example, a dimethylene group.

[0322] In one mode, R b3 It is a single bond.

[0323] In another aspect, R b3 C that can be substituted 1-6 It is an alkylene group, preferably C 1-6 It is an alkylene group.

[0324] Among the above formulas, R a is, alkyl, phenyl, -SR a1 , -OR a2 , -NR a3 2,

[0325]

[0326] is. R a It may be part of the so-called RAFT system.

[0327] Among the above formulas, R a1 , R a2 , R a3 , R a4 , R a5 and R a6 Each is independently an alkyl group or a phenyl group.

[0328] The above R a1 Silver, preferably C 1-20 Alkyl group, more preferably C 3-18 Alkyl group, more preferably C 4-12 It is an alkyl group.

[0329] The above R a2 is preferably a phenyl group or C 1-20 It is an alkyl group. Corresponding C 1-20 The alkyl group is preferably C 1-10 Alkyl group, more preferably C 1-6 Alkyl group, more preferably C 1-3 It is an alkyl group.

[0330] The above R a3 Silver, preferably C 1-20 Alkyl group, more preferably C 1-10 Alkyl group, more preferably C 1-6 alkyl group, more preferably C 1-3 It is an alkyl group.

[0331] The above R a4 is, preferably C 1-6 Alkyl group, more preferably C 1-3 It is an alkyl group, more preferably a methyl group.

[0332] The above R a5 is, preferably C 1-6 Alkyl group, more preferably C 1-3 It is an alkyl group, more preferably a methyl group.

[0333] The above R a6 Silver, preferably C1-6 Alkyl group, more preferably C 1-3 It is an alkyl group, more preferably a methyl group.

[0334] The above R a7 It is silver, hydrogen, or a halogen atom (e.g., fluorine, chlorine, bromine, or iodine, preferably chlorine).

[0335] In one mode, R a is, -SR a1 or -OR a2 am.

[0336] In one embodiment, (A) the fluoropolyether group-containing polymer may be a fluoropolyether group-containing polymer represented by formula (1).

[0337] In one embodiment, (A) the fluoropolyether group-containing polymer may be a fluoropolyether group-containing polymer represented by formula (2).

[0338] The number average molecular weight of the above fluoropolyether group-containing polymer is not particularly limited, but is 2×10 2 Up to 1×10 5 , preferably 1×10 3 Up to 5×10 4 , more preferably 3×10 3 Up to 2×10 4 It can be. By having a number average molecular weight in this range, the solubility in solvents and the contact angle of the surface treatment layer can be increased. The number average molecular weight can be obtained by gel permeation chromatography (GPC).

[0339] The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the above fluoropolyether group-containing polymer may preferably be 3.0 or less, more preferably 2.5 or less, even more preferably 2.0 or less, and even more preferably 1.5 or less. By reducing the polydispersity, a more homogeneous surface treatment layer can be formed, and the durability of the surface treatment layer can be improved.

[0340] The above fluoropolyether group-containing polymer can be synthesized, for example, using so-called RAFT (Reversible addition-fragmentation chain transfer) type radical polymerization.

[0341] First, a RAFT agent having a perfluoropolyether group is prepared. For example, a compound (A) having a perfluoropolyether and a compound (B1) or (B2) having a RAFT backbone (-SC(=S)-):

[0342]

[0343] [In the middle of the meal, R a , R F1 , R F2 , X a and X b is the same meaning as above;

[0344] L 1 and L 2 is, respectively, the talli part.]

[0345] By reacting with a chain transfer agent (1a) or (2a) having a perfluoropolyether group:

[0346]

[0347] [In the middle of the meal, R a , R F1 , R F2 , X a and X b is the same meaning as above.]

[0348] You can obtain.

[0349] By reacting the chain transfer agent (1a) or (2a) obtained above with a monomer having an unsaturated bond, a compound represented by formula (1) or (2) can be obtained. This reaction is a so-called RAFT polymerization, and the reaction conditions can be those generally used in RAFT polymerization.

[0350] [(B) Siloxane Polymer]

[0351] The above siloxane polymer is of the following formula:

[0352]

[0353] [During the meal:

[0354] R 21 Silver, independently in each appearance, hydrogen atom, C 1-6 It is an alkyl group or an aryl group, and

[0355] R 22 is, independently in each appearance, a hydrogen atom, C 1-6 It is an alkyl group or an aryl group, and

[0356] R 23 Silver, hydrogen atom, C 1-6 It is an alkyl group or an aryl group, and

[0357] R 24 is, hydrogen atom, C 1-6 It is an alkyl group or an aryl group, and

[0358] R 25 is a hydrogen atom or a monovalent organic group, and

[0359] R 26 It is silver, a hydrogen atom, or a monovalent organic group, and

[0360] p is an arbitrary integer.

[0361] It is a siloxane polymer represented as.

[0362] Among the above formulas, R 21 and R 22 is, independently in each appearance, a hydrogen atom, C 1-6 It is an alkyl group or an aryl group.

[0363] Among the above formulas, R 23 and R 24 are, each independently, hydrogen atoms, C 1-6 It is an alkyl group or an aryl group.

[0364] R 21 , R 22 , R 23 and R 24is both the same contribution and a different contribution. In a preferred mode, R 21 , R 22 , R 23 and R 24 is the same thing.

[0365] The above C 1-6 The alkyl group may be a straight chain or a branched chain. In addition, the above C 1-6 The alkyl group may include a cyclic structure. In one embodiment, the C thereof 1-6 The alkyl group is a straight chain. In another embodiment, the C 1-6 The alkyl group is a branched chain. In another embodiment, the C 1-6 The alkyl group is C 3-6 It is a cyclic alkyl group.

[0366] The above C 1-6 The alkyl group is preferably C 1-4 Alkyl group, more preferably C 1-3 It is an alkyl group, more preferably a methyl group or an ethyl group, particularly preferably a methyl group.

[0367] The above aryl group may be a single ring or a polycyclic ring.

[0368] The above aryl group is preferably C 5-20 aryl group, more preferably C 6-16 aryl group, more preferably C 6-12 aryl group, more preferably C 6-10 It is Arilgi.

[0369] In one mode, R 21 , R 22 , R 23 and R 24 is a hydrogen atom.

[0370] In another aspect, R 21 , R 22 , R 23 and R 24 is, C 1-6 alkyl group, or aryl group, preferably C 1-6 It is an alkyl group.

[0371] The above R 25 and R 26 Each is independently a hydrogen atom or a monovalent organic group.

[0372] The above monovalent organic group is preferably -R 27 -R 28 am.

[0373] The above R 27 Eun comprises the siloxane backbone of the above siloxane polymer and the terminal functional group R 28 It is interpreted as part of the linker connecting. Therefore, R 27 Any divalent organic group can exist as long as the above siloxane polymer can exist stably.

[0374] The above R 27 It is a divalent organic group, an oxygen atom, or a single bond.

[0375] In one embodiment, the above-mentioned divalent organic group is,

[0376]

[0377] [During the meal:

[0378] R 51 and R 53 은, each independently, -(CH2) r1 - or o-, m- or p-phenylene group, preferably -(CH2) r1 - and,

[0379] r1 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and

[0380] R 52 is, independently in each appearance, -O-, -S-, o-, m- or p-phenylene group, -C(O)O-, -CONR 54 -, -O-CONR 54 -, -NR 54 - and -(CH2) r2 It is a group selected from a group consisting of -, and

[0381] R 54is, independently in each appearance, a hydrogen atom, a phenyl group, C 1-6 It is an alkyl group (preferably a methyl group) or an oxyalkylene containing group having 1 to 10 carbon atoms, and

[0382] r2 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and

[0383] q5 is 0 or 1, and

[0384] q6 is an integer from 0 to 10, preferably an integer from 0 to 5, more preferably an integer from 0 to 3, and

[0385] q7 is 0 or 1, and

[0386] Provided that at least one of q5, q6, and q7 is 1.

[0387] Examples of divalent organic groups represented as can be found.

[0388] The above R 27 Silver, preferably single bonds, oxygen bonds, formula:

[0389]

[0390] [During the meal:

[0391] R 51 and R 53 은, each independently, -(CH2) r1 - or representing an o-, m- or p-phenylene group, preferably -(CH2) r1 - and,

[0392] r1 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and

[0393] R 61 ...in each appearance, independently -O-, -S-, -C(O)O-, -CONR 54 -, -O-CONR 54 - and -NR 54 A group selected from the group consisting of -, preferably -O-, and

[0394] q5 is 0 or 1, and

[0395] q6 is an integer from 0 to 10, preferably an integer from 0 to 5, more preferably an integer from 0 to 3, and

[0396] q7 is 0 or 1, and

[0397] Provided that at least one of q5, q6, and q7 is 1.

[0398] It is a device indicated as.

[0399] The above R 28 It is a hydrogen atom, -OH, -CO-CH=CH2, -CO-C(CH3)=CH2, epoxy group, alicyclic epoxy group, amino group, carboxyl group, vinyl group, alkoxy group, or thiol group.

[0400] In a preferred embodiment, the above R 28 It is silver, hydrogen atom, -OH, -CO-CH=CH2, or -CO-C(CH3)=CH2.

[0401] In one mode, R 25 and R 26 silver, C 1-6 Alkyl group, preferably C 1-3 It is an alkyl group.

[0402] In a desirable embodiment,

[0403] R 25 is C 1-6 It is an alkyl group, and

[0404] R 26 silver, -R 27 -R 28 And,

[0405] R 27 It is silver, a divalent organic group, an oxygen atom, or a single bond, and

[0406] R 28 It is a hydrogen atom, -OH, -CO-CH=CH2, -CO-C(CH3)=CH2, epoxy group, alicyclic epoxy group, amino group, carboxyl group, vinyl group, alkoxy group, or thiol group.

[0407] In another desirable embodiment,

[0408] R 25 and R 26 silver, -R 27 -R 28 And,

[0409] R 27 It is silver, a divalent organic group, an oxygen atom, or a single bond, and

[0410] R 28 It is a hydrogen atom, -OH, -CO-CH=CH2, -CO-C(CH3)=CH2, epoxy group, alicyclic epoxy group, amino group, carboxyl group, vinyl group, alkoxy group, or thiol group.

[0411] The number average molecular weight of the above siloxane polymer is greater than 350 and less than 10,000, preferably 800 to 8,000, more preferably 900 to 7,000. By setting the number average molecular weight of the above siloxane polymer to the above range, the surface slipperiness and appearance of the surface treatment layer obtained by the composition of the present disclosure are improved.

[0412] The content of the above siloxane polymer is 0.1 to 300 parts by mass, preferably 1 to 300 parts by mass, more preferably 1 to 250 parts by mass, even more preferably 1 to 200 parts by mass, and particularly preferably 1 to 150 parts by mass, based on 100 parts by mass of the above fluoropolyether group-containing polymer.

[0413] [Other ingredients]

[0414] The composition of the present disclosure may also contain a (non-reactive) fluoropolyether compound, preferably a perfluoro(poly)ether compound, which can also be understood as a fluorine-containing oil (hereinafter collectively referred to as "fluorine-containing oil"). In addition, the composition of the present disclosure may include other components such as a solvent, an active energy beam radical curing initiator, a thermal acid generator, and an active energy beam cationic curing initiator.

[0415] The above fluorine-containing oil is not particularly limited, but, for example, a compound represented by the following general formula (3) (perfluoro(poly)ether compound) may be used.

[0416]

[0417] During the meal, Rf 5 is a carbon-1 to 16 alkyl group that may be substituted by one or more fluorine atoms (preferably, C 1-16 Representing the perfluoroalkyl group), and Rf 6 A carbon-1 to 16 alkyl group that may be substituted by one or more fluorine atoms (preferably, C 1-16 (perfluoroalkyl group), representing a fluorine atom or a hydrogen atom, Rf 5 and Rf 6 More preferably, independently, C 1-3 It is a perfluoroalkyl group.

[0418] a', b', c', and d' each represent the number of repeating units of four types of perfluoro(poly)ethers constituting the main backbone of the polymer, and are independently integers from 0 to 300, and the sum of a', b', c', and d' is at least 1, preferably 1 to 300, more preferably 20 to 300. The order of existence of each repeating unit enclosed in parentheses with the subscripts a', b', c', or d' is arbitrary in the formula. Among these repeating units, -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)- and (OCF2CF(C2F5))-, but preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)- and (OCF2CF(CF3))-, and preferably -(OCF2CF2CF2)-. -(OC2F4)- may be either -(OCF2CF2)- or (OCF(CF3))-, but preferably -(OCF2CF2)-.

[0419] Examples of perfluoro(poly)ether compounds represented by the above general formula (3) include compounds represented by any of the following general formulas (3a) and (3b) (one or a mixture of two or more).

[0420]

[0421] Among these formulas, Rf 5 and Rf 6The above is as described above; in Equation (3a), b" is an integer between 1 and 100; and in Equation (3b), a" and b" are each independently integers between 0 and 30, and c" and d" are each independently integers between 1 and 300. The order of existence of each repeating unit enclosed in parentheses with subscripts a", b", c", and d" is arbitrary in the expression.

[0422] In addition, from another perspective, fluorine-containing oils, general formula Rf 3 -F(in the food, Rf 3 C 5-16 It may be a compound represented by a perfluoroalkyl group. In addition, it may be a chlorotrifluoroethylene oligomer.

[0423] The above fluorine-containing oil may have an average molecular weight of 500 to 10,000. The molecular weight of the fluorine-containing oil can be measured using GPC.

[0424] Fluorine-containing oil may be included in the composition of the present disclosure in an amount of, for example, 0 to 50 mass%, preferably 0 to 30 mass%, and more preferably 0 to 5 mass%. In one embodiment, the composition of the present disclosure does not substantially contain fluorine-containing oil. Substantially not containing fluorine-containing oil means not containing fluorine-containing oil at all, or may contain trace amounts of fluorine-containing oil.

[0425] In one embodiment, the average molecular weight of the fluorine-containing oil may be greater than the average molecular weight of the fluoropolyether group-containing silane compound. By using such an average molecular weight, superior wear resistance and surface slipperiness can be obtained, particularly when forming a surface treatment layer by vacuum deposition.

[0426] In one embodiment, the average molecular weight of the fluorine-containing oil may be smaller than the average molecular weight of the fluoropolyether group-containing silane compound. By using such an average molecular weight, it is possible to form a cured product having high wear resistance and high surface slipperiness while suppressing the reduction of transparency of the surface treatment layer obtained from such compounds.

[0427] Fluorine-containing oil contributes to improving the surface slipperiness of the layer formed by the composition of the present disclosure.

[0428] As the above solvent, fluorine-containing organic solvents and fluorine-free organic solvents may be used.

[0429] As the above-mentioned fluorine-containing organic solvent, for example, perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecalin, perfluoroalkylethanol, perfluorobenzene, perfluorotoluene, perfluoroalkylamine (Fluorinert (trade name) etc.), perfluoroalkyl ether, perfluorobutyltetrahydrofuran, polyfluoroaliphatic hydrocarbon (Asahiclean AC6000 (trade name)), hydrochlorofluorocarbon (Asahiclean AK-225 (trade name) etc.), hydrofluoroether (Novec (trade name), HFE-7100 (trade name) etc.), 1,1,2,2,3,3,4-heptafluorocyclopentane, fluorine-containing alcohol, perfluoroalkyl bromide, perfluoroalkyl iodide, perfluoropolyether (Krytox (trade name), Demnum (trade name), Pombulin (trade name) etc.), 1,3-bistrifluoromethylbenzene, Examples include 2-(perfluoroalkyl)ethyl methacrylate, 2-(perfluoroalkyl)ethyl acrylate, perfluoroalkylethylene, Freon (134a) and hexafluoropropene oligomer.

[0430] In addition, as the above-mentioned fluorine-free organic solvent, for example, acetone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether pentane, hexane, heptane, octane, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, carbon disulfide, benzene, toluene, xylene, nitrobenzene, diethyl ether, dimethoxyethane, diglyme, triglyceride, ethyl acetate, butyl acetate, dimethylformamide, dimethyl sulfoxide, 2-butanone, acetonitrile, benzonitrile, butanol, 1-propanol, Examples include 2-propanol, ethanol, methanol, and diacetone alcohol.

[0431] The above solvent may be used as a single type or in combination of two or more types.

[0432] The above solvent is included in an amount of 5 to 100,000 parts by mass, preferably 5 to 50,000 parts by mass, with respect to 100 parts by mass of the total of the above fluoropolyether group-containing polymer and siloxane polymer and, if present, the following fluorine-containing oil (C).

[0433] As the above active energy beam radical curing initiator, for example, it generates radicals for the first time by irradiating electromagnetic waves in a wavelength range of 350 nm or less, i.e., ultraviolet rays, electron beams, X-rays, γ-rays, etc., and acts as a catalyst to initiate the curing (crosslinking reaction) of the curable portions (e.g., carbon-carbon double bonds) of the fluoropolyether group-containing polymer, and typically uses one that generates radicals with ultraviolet rays.

[0434] The above active energy beam radical curing initiator is appropriately selected according to the type of curable site in the fluoropolyether group-containing polymer, the type of active energy beam used (wavelength range, etc.), and the irradiation intensity, but generally, as an initiator for curing the fluoropolyether group-containing polymer having a radically reactive curable site (carbon-carbon double bond) using an active energy beam in the ultraviolet region, the following may be exemplified.

[0435] ㆍAcetophenone series

[0436] Acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, hydroxypropiophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, etc.

[0437] ㆍBenzoin-based

[0438] Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0439] ㆍBenzophenone series

[0440] Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxypropylbenzophenone, acrylated benzophenone, mihiller ketone, etc.

[0441] Thioxanthones

[0442] Thioxanthone, chlorothioxanthone, methylthioxanthone, diethylthioxanthone, dimethylthioxanthone, etc.

[0443] Others

[0444] Benzyl, α-acyloxime esters, acylphosphine oxide, glyoxyesters, 3-ketocoumarins, 2-ethylanthraquinone, camphoquinone, anthraquinone, etc.

[0445] These active energy beam curing initiators may be used as a single type or in combination of two or more types.

[0446] The above active energy beam curing initiator is not particularly limited, but is included in an amount of 0.01 to 1,000 parts by mass, preferably 0.1 to 500 parts by mass, per 100 parts by mass of the total of the above fluoropolyether group-containing polymer, the siloxane polymer, and, if present, the fluorine-containing oil.

[0447] By using the above-mentioned thermal acid generating agent, a decomposition reaction of a compound containing a cationic species occurs due to heat, initiating the curing (crosslinking reaction) of a curable portion (e.g., a cyclic ether) of a polymer containing a fluoropolyether group having a curable portion.

[0448] As the above-mentioned thermal acid generating agent, for example, the following general formula (a):

[0449]

[0450] (In the formula, Z represents at least one element selected from the group consisting of S, Se, Te, P, As, Sb, Bi, O, N, and halogen elements. R 1 , R 2 , R 3 and R 4 is identical or different and represents an organic group. a, b, c, and d are 0 or positive, and the sum of a, b, c, and d is equal to the valence of Z. Cation (R 1 a R 2 b R 3 c R 4 d Z) +mA represents an onium salt. A represents a metal element or metalloid that is the central atom of the halide complex, and is at least one selected from the group consisting of B, P, As, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co. X represents a halogen element. m is the net charge of the halide complex ion. n is the number of halogen elements in the halide complex ion.) Compounds represented by this form are suitable.

[0451] The anion (AX) of the above general formula (a) n ) -m As a specific example of, tetrafluoroborate (BF4 - ), hexafluorophosphate (PF6 - ), hexafluoroantimonate (SbF6 - ), hexafluoroarsenate (AsF6 - ), hexachloroantimonate (SbCl6 - Examples include ). Also, the general formula AXn(OH) - Anions represented by may also be used. In addition, other anions include perchlorate ions (ClO4). - ), trifluoromethylsulfite ion (CF3SO3 - ), fluorosulfonate ion (FSO3 - Examples include toluenesulfonate ions, trinitrobenzenesulfonate ions, etc.

[0452] Specific products of the above-mentioned thermal acid generators include, for example, diazonium salt types such as the AMERICURE series (manufactured by American Can), ULTRASET series (manufactured by Adeka), and WPAG series (manufactured by Wako Junyaku); iodium salt types such as the UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicon), Photoinitiator 2074 (manufactured by Longfrain), and WPI series (manufactured by Wako Junyaku); Examples include sulfonium salt types such as the CYRACURE series (Union Carbide), UVI series (General Electric), FC series (3M), CD series (Satomer), Optoma SP series and Optoma CP series (Adeka), San-Aid SI series (Sanshin Kagaku Kogyo), CI series (Nippon Soda), WPAG series (Wako Junyaku), and CPI series (San Afro).

[0453] These heat-generating agents may be used as a single type or in combination of two or more types.

[0454] The above-mentioned thermal acid generating agent is not particularly limited, but is included in an amount of 0.01 to 1,000 parts by mass, preferably 0.1 to 500 parts by mass, per 100 parts by mass of the total of the fluoropolyether group-containing polymer and siloxane polymer, and, if present, the fluorine-containing oil.

[0455] By using the above active energy beam cationic curing initiator, a compound containing cationic species is excited by light, causing a photodecomposition reaction to occur, thereby initiating the curing (crosslinking reaction) of the curable sites (e.g., cyclic ethers) of a polymer containing fluoropolyether groups.

[0456] Suitable for the above active energy beam cation curing initiator are, for example, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate, p-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluoroantimonate, (2,4-cyclopentadiene-1-yl)[(1-methylethyl)benzene]-Fe-hexafluoroantimonate, diallyl iodonium hexafluoroantimonate, etc.

[0457] Specific products of the above active energy beam cation curing initiators include, for example, UVI-6950, UVI-6970, UVI-6974, UVI-6990 (manufactured by Union Carbide); Adeka Optoma SP-150, SP-151, SP-170, SP-172 (manufactured by ADEKA); Irgacure 250 (manufactured by Shiba Japan); CI-2481, CI-2624, CI-2639, CI-2064 (manufactured by Nippon Soda); CD-1010, CD-1011, CD-1012 (manufactured by Satomer); DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 (manufactured by Midori Kagaku); Diazonium salt type, iodonium salt type, sulfonium salt type, etc., such as PCI-061T, PCl-062T, PCl-020T, PCl-022T (manufactured by Nippon Kagaku Co., Ltd.); CPl-100P, CPT-101A, CPI-200K (manufactured by San Apro Co., Ltd.); San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L, San-Aid ST-110L, San-Aid SI-145, San-Aid SI-150, San-Aid SI-160, San-Aid SI-180L (manufactured by Sanshin Kagaku Kogyo Co., Ltd.); and WPAG series (manufactured by Wako Junyaku Co., Ltd.) are preferred.

[0458] These active energy beam cation curing initiators may be used as a single type or in combination of two or more types.

[0459] The above active energy beam radical curing initiator is not particularly limited, but is included in an amount of 0.01 to 1,000 parts by mass, preferably 0.1 to 500 parts by mass, per 100 parts by mass of the total of the fluoropolyether group-containing polymer and siloxane polymer, and, if present, the fluorine-containing oil.

[0460] [Surface Treatment Agent]

[0461] The composition of the present disclosure is useful as a surface treatment agent. Accordingly, the present disclosure provides a surface treatment agent comprising the composition of the present disclosure.

[0462] In a preferred embodiment, the composition of the present disclosure is a surface treatment agent.

[0463] [Curable composition]

[0464] The present disclosure provides a curable composition comprising the composition of the present disclosure, a surface treatment agent, and / or a matrix-forming composition.

[0465] [Composition forming a matrix]

[0466] The composition forming the matrix above refers to a composition containing a compound having at least one carbon-carbon double bond, for example, but not specifically limited, monofunctional and / or polyfunctional acrylates and methacrylates (hereinafter, acrylates and methacrylates are collectively referred to as "(meth)acrylates"), monofunctional and / or polyfunctional urethane (meth)acrylates, and monofunctional and / or polyfunctional epoxy (meth)acrylates. The composition forming the matrix is ​​not specifically limited, but is generally a composition that serves as a hard coating agent or an anti-reflective agent, and examples include a hard coating agent containing a polyfunctional (meth)acrylate or an anti-reflective agent containing a fluorine-containing (meth)acrylate. The hard coating agent in question is marketed, for example, by Arakawa Kagaku Kogyo Co., Ltd. as Beam Set 502H, 504H, 505A-6, 550B, 575CB, 577, and 1402 (product names), by Daicel Scitec as EBECRYL40 (product name), and by Yokohama Rubber as HR300 series (product name). The anti-reflective agent in question is marketed, for example, by Daikin Kogyo Co., Ltd. as Optool AR-110 (product name).

[0467] As a composition forming the above matrix, a composition containing a monofunctional and / or polyfunctional epoxy compound is also preferred. For example, epoxy compounds such as bisphenol A diglycidyl ether, 2,2'-bis(4-glycidyloxycyclohexyl)propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5,5-spiro-(3,4-epoxycyclohexane)-1,3-dioxane, bis(3,4-epoxycyclohexyl)adipate, 1,2-cyclopropane dicarboxylic acid bisglycidyl ester, and triglycidyl isocyanurate may be used. In addition, although overlapping with the above, hydrogenated epoxy resin, alicyclic epoxy resin, or epoxy resin containing an isocyanurate ring, or bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenolaralkyl type epoxy resin, biphenylaralkyl type epoxy resin, hydrogenated epoxy resin in which the aromatic ring of the above various epoxy resins is hydrogenated, or dicyclopentadiene type epoxy resin may be used.

[0468] In one embodiment, the curable composition contains a fluoropolyether group-containing polymer and a siloxane polymer in an amount of 0.01 to 20 mass%, preferably 0.01 to 10 mass%, more preferably 0.1 to 10 mass%, with respect to the solid content of the matrix-forming composition.

[0469] The curable composition of the present disclosure may also include antioxidants, thickeners, leveling agents, defoaming agents, antistatic agents, antifogging agents, ultraviolet absorbers, pigments, dyes, inorganic fine particles such as silica, aluminum paste, talc, glass frit, metal powder, and fillers, polymerization inhibitors such as butylated hydroxytoluene (BHT) and phenothiazine (PTZ).

[0470] [article]

[0471] Next, the articles of the present disclosure will be described.

[0472] The present disclosure provides an article comprising a substrate and a layer (surface treatment layer) formed on the surface of said substrate by the composition of the present disclosure, a surface treatment agent, or a curable composition. This article may be manufactured, for example, as follows.

[0473] First, a substrate is prepared. The substrates available for use in the present disclosure may be composed of any suitable material, such as glass, resin (natural or synthetic resin, for example, general plastic materials, preferably polycarbonate resin, poly(meth)acrylate resin, polyethylene terephthalate resin, triacetylcellulose resin, polyimide resin, modified (transparent) polyimide resin, polycycloolefin resin, polyethylene naphthalate resin, and may be in the form of a plate, film, or other forms), metal (single metal such as aluminum, copper, silver, iron, etc., or a composite such as an alloy), ceramics, semiconductor (silicon, germanium, etc.), fiber (textile, nonwoven fabric, etc.), fur, leather, wood, porcelain, stone, building material, etc.

[0474] For example, if the article to be manufactured is an optical component, the material constituting the surface of the substrate may be a material for optical components, such as glass or transparent plastic. In addition, depending on the specific specifications, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), a vaporizing film layer, a hard coating film layer, a polarizing film, a phase difference film, an organic EL display module, and a liquid crystal display module.

[0475] The shape of the substrate is not particularly limited. In addition, the surface area of ​​the substrate on which the surface treatment layer is to be formed may be at least a part of the substrate surface and can be appropriately determined according to the use and specific specifications of the article to be manufactured.

[0476] Next, a film of the composition, surface treatment agent, or curable composition of the above-described present disclosure is formed on the surface of such substrate, and the film is post-treated as necessary, thereby forming a surface treatment layer of the composition, surface treatment agent, or curable composition of the present disclosure.

[0477] Film formation of the composition, surface treatment agent, or curable composition of the present disclosure can be carried out by applying the composition, surface treatment agent, or curable composition to the surface of a substrate to coat the said surface. The coating method is not particularly limited. For example, a wet coating method may be used.

[0478] Examples of wet coating methods include immersion coating, spin coating, flow coating, spray coating, roll coating, gravure coating, micro-gravure coating, bar coating, die coating, screen printing, and similar methods.

[0479] When using a wet coating method, the composition, surface treatment agent, or curable composition of the present disclosure may be diluted with a solvent and then applied to the surface of a substrate. As the solvent, the above-mentioned fluorine-containing organic solvent and fluorine-free organic solvent may be used.With regard to the stability of the compositions, surface treatment agents, or curable compositions of the present disclosure and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons; Hydrofluoroethers (HFE) (e.g., alkyl perfluoroalkyl ethers such as perfluoropropylmethyl ether (C3F7OCH3), perfluorobutylmethyl ether (C4F9OCH3), perfluorobutylethyl ether (C4F9OC2H5), perfluorohexylmethyl ether (C2F5CF(OCH3)C3F7) (the perfluoroalkyl group and the alkyl group may be straight-chain or branched)), hydrochlorofluorocarbons (Asahi Clean AK-225 (trade name) etc.), cellosolve-based solvents such as methylcellosolve, ethylcellosolve, methylcellosolve acetate, ethylcellosolve acetate; Ester-based solvents such as diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, ethyl acetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, 3-methyl methoxypropionate, 3-ethyl methoxypropionate, 2-methyl hydroxyisobutyrate, 2-ethyl hydroxyisobutyrate; propylene glycol-based solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether; Ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylamino ketone, 2-heptanone; alcohol-based solvents such as methanol, ethanol, propanol, isopropanol, butanol, diacetone alcohol; aromatic hydrocarbons such as toluene, xylene, etc. These solvents may be used alone or as a mixture of two or more.Among these, hydrofluoroethers, glycol-based solvents, ester-based solvents, ketone-based solvents, and alcohol-based solvents are preferred, and perfluorobutylmethyl ether (C4F9OCH3) and / or perfluorobutylethyl ether (C4F9OC2H5), propylene glycol monomethyl ether, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, isopropanol, butanol, and diacetone alcohol are particularly preferred.

[0480] Next, the film is post-treated. This post-treatment is not particularly limited, but is performed by irradiating, for example, with active energy rays, such as electromagnetic waves in the wavelength range of 350 nm or less, i.e., ultraviolet rays, electron beams, X-rays, γ-rays, etc. Or it is performed by heating for a predetermined time. By performing this post-treatment, curing is initiated in the curable portions of the fluoropolyether group-containing polymer and, if present, the curable portions of the composition forming the matrix, and bonds are formed between these compounds and between these compounds and the substrate.

[0481] In accordance with the above, a surface treatment layer derived from the composition, surface treatment agent, or curable composition of the present disclosure is formed on the surface of a substrate, and an article of the present disclosure is manufactured. The surface treatment layer obtained by this has both high surface slipperiness (or lubricity, for example, the ability to wipe off contaminants such as fingerprints, or an excellent tactile sensation to fingers) and high frictional durability. Furthermore, in addition to high frictional durability and surface slipperiness, this surface treatment layer may have water repellency, oil repellency, and antifouling properties (for example, preventing the adhesion of contaminants such as fingerprints), depending on the composition of the composition, surface treatment agent, or curable composition used, and can be suitably used as a functional thin film.

[0482] The kinetic friction coefficient of the film formed by the surface treatment composition of the present invention is preferably 0.85 or less, more preferably 0.80 or less, and even more preferably 0.77 or less. By lowering the kinetic friction coefficient, a coating film having a better tactile feel can be produced.

[0483] The above kinetic friction coefficient can be measured using a friction measuring instrument ("Tribomaster TL201Ts, manufactured by Trinity Lab Co., Ltd."), using a tactile contactor as the frictional element, with a load of 20 gf and a scanning speed of 10 mm / sec.

[0484] The range of the water static contact angle of the film formed by the surface treatment composition of the present invention is preferably 111 degrees or more, more preferably 112 degrees or more, and even more preferably 113 degrees or more. By increasing the contact angle, a coating film with superior antifouling properties can be produced.

[0485] The above contact angle can be measured with an accumulation amount of 2 μL using a contact angle meter (Kyowa Kaimen Kagaku Co., Ltd., “DropMaster”), etc.

[0486] The present disclosure also relates to an optical material having the surface treatment layer on the outermost layer.

[0487] As optical materials, in addition to optical materials related to displays such as those exemplified later, various other optical materials may be preferably cited: for example, displays such as cathode ray tubes (CRT; e.g., TVs, personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, back-projection displays, fluorescent display tubes (VFDs), and field emission displays (FEDs), or protective plates, films, or surfaces of such displays that have been treated with an anti-reflective coating.

[0488] In one embodiment, an article having a surface treatment layer obtained by the present disclosure may be an optical member, although not particularly limited. Examples of optical members include the following: lenses such as eyeglasses; front surface protection plates, anti-shatter films, anti-reflective plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and portable information terminals; disc surfaces of optical discs such as Blu-ray (Blu-ray (registered trademark)) discs, DVD discs, CD-Rs, MOs, etc.; optical fibers, etc.

[0489] In one embodiment, articles having a surface treatment layer obtained by the present disclosure may include, for example, LiDAR (Light Detection and Ranging) cover members, sensor members, instrument panel cover members, automotive interior members, and the like, particularly those of these members for automobiles.

[0490] The thickness of the surface treatment layer is not particularly limited. In the case of an optical member, the thickness of the surface treatment layer is preferably in the range of 0.1 to 30 μm, preferably 0.5 to 20 μm, in terms of optical performance, surface slipperiness, frictional durability, and antifouling properties.

[0491] The foregoing has described in detail articles obtained using the compositions, surface treatment agents, or curable compositions of the present disclosure. Furthermore, the uses, methods of use, and methods of manufacturing articles of the compositions, surface treatment agents, or curable compositions of the present disclosure are not limited to those exemplified above.

[0492] Examples

[0493] The present disclosure is described below in terms of examples, but the present disclosure is not limited to the following examples. Furthermore, in the present examples, the chemical formulas shown below all represent average compositions, and the order of existence of repeating units ((OCF2CF2CF2), (OCF2CF2), (OCF2), etc.) constituting the perfluoropolyether is arbitrary.

[0494] 1. Synthesis of Perfluoropolyether-Containing Chain Transfer Agents

[0495] Synthesis Example 1

[0496] Synthesis of Chain Transfer Agent (A-1)

[0497] In a flask, 0.505 g of 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid (Fujifilm Wako Junyaku Co., Ltd.), 0.019 g of 4-dimethylaminopyridine (DMAP) (Tokyo Kasei High School Co., Ltd.), 0.293 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI) (Tokyo Kasei High School Co., Ltd.), and CF3CF2CF2 (OCF2CF2CF2) n 5.0 g of alcohol containing a perfluoropolyether represented by OCF2CF2CH2OH (average value of n ≈ 25) (manufactured by Daikin Kogyo Co., Ltd.) was taken, 13 mL of Asahi Clean AK-225 (manufactured by AGC Co., Ltd.) was added, and the mixture was stirred at room temperature to carry out the reaction. After stirring overnight, the reaction solution was washed with saturated sodium bicarbonate water and saline solution. The organic layer was separated and concentrated, and added dropwise to methanol to obtain 4.56 g of a yellow oily target product (A-1).

[0498] 2. Synthesis of PFPE block polymers having epoxy groups

[0499] Synthesis Example 2

[0500] (1) Synthesis of PFPE block polymer (P-1) having epoxy groups

[0501] 1.0 g of chain transfer agent (A-1), 0.23 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE) (Mitsubishi Chemical Co., Ltd.), and 12 mg of N,N'-azobisisobutyronitrile (AIBN) (Fujifilm Wako Junyaku Co., Ltd.) were added to a reaction vessel and dissolved in 2.9 mL of 1,3-bis(trifluoromethyl)benzene (Tokyo Kasei Kogyo Co., Ltd.). The mixture was heated at 75°C for 17 hours, and the reaction solution was added dropwise to hexane to precipitate and recover the block polymer (P-1). From NMR measurements, the degree of polymerization of 4HBAGE was calculated to be 5.

[0502] Synthesis Example 3

[0503] (2) Synthesis of PFPE block polymer (P-2) having epoxy groups

[0504] A block polymer (P-2) of 4HBAGE with a degree of polymerization of 10 was synthesized by performing the same procedure as in Synthesis Example 2 and changing the amount of 4HBAGE added to 0.46g.

[0505] 3. Synthesis of PFPE block polymer having (meth)acrylic groups

[0506] Synthesis Example 4

[0507] (1) Synthesis of PFPE block polymer (P-3) having hydroxyl groups

[0508] 1.3 g of (A-1), 0.18 g of 2-hydroxyethyl acrylate (HEA) (manufactured by Tokyo Kasei High School Co., Ltd.), and 15.5 mg of AIBN were added to a reaction vessel and dissolved in 2.1 mL of 1,3-bis(trifluoromethyl)benzene. Polymerization was carried out by heating at 70°C for 22.5 hours to obtain a solution of block polymer (P-3). From NMR measurement, the degree of polymerization of HEA was calculated to be 5.

[0509] Synthesis Example 5

[0510] (2) Synthesis of PFPE block polymer (P-4) having acrylic groups

[0511] To the reaction solution of (1), 1.1 equivalents of karens AOI (manufactured by Showa Denko Co., Ltd.) and 0.01 equivalents of dibutyltin dilaurate (DBTDL) (manufactured by Tokyo Kasei High School Co., Ltd.) were added to the HEA unit of the polymer (P-3), and the mixture was stirred at 40°C for 2 hours. After confirming that the hydroxyl group was 100% reacted by NMR measurement, the reaction solution was dropped into methanol to precipitate and recover the block polymer (P-4) having an acrylic group.

[0512] Synthesis Example 6

[0513] (3) Synthesis of PFPE block polymer (P-5) having methacrylate groups

[0514] A block polymer (P-5) having methacrylate groups was synthesized in the same manner as (2) of Synthesis Example 5, except that the karens AOI was changed to a karens MOI (manufactured by Showa Denko Co., Ltd.).

[0515] Comparative Synthesis Example 1

[0516] 4. Synthesis of PFPE compounds (P-6) containing acrylic groups

[0517] In a 1L 4-neck flask equipped with a dropping funnel, condenser, thermometer, and stirring device, Sumidur (registered trademark) N3300 (Sumika Bayer Urethane Co., Ltd., NCO group content 21.8%, 36.6g) was dissolved in Asahi Clean AK-225 (219.4g), dibutyltin dilaurate (Fujifilm Wako Junyaku Co., Ltd., 0.30g) was added, and under a nitrogen stream at 40°C while stirring, average composition: CF3CF2CF2O(CF2CF2CF2O) 14A solution of alcohol (60.0 g) containing a perfluoropolyether represented as CF2CF2CH2OH dissolved in Asahi Clean AK-225 (60.0 g) was added dropwise and stirred. HEA (19.6 g) was added dropwise and stirred. It was confirmed that the absorption of NCO was completely eliminated in the IR. 0.05 g of dibutylhydroxytoluene was added to completely remove the solvent, and an acrylic group-containing PFPE compound (P-6) was synthesized.

[0518] Synthesis Example 7

[0519] 5. Synthesis of PFPE block polymer (P-7) having epoxy groups

[0520] 1.0 g of chain transfer agent (A-1), 0.20 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE) (Mitsubishi Chemical Co., Ltd.), 0.10 g of n-butyl acrylate (Tokyo Kasei Co., Ltd.), and 12 mg of N,N'-azobisisobutyronitrile (AIBN) (Fujifilm Wako Junyaku Co., Ltd.) were added to a reaction vessel and dissolved in 3.1 mL of 1,3-bis(trifluoromethyl)benzene (Tokyo Kasei Co., Ltd.). The mixture was heated at 75°C for 20 hours, and the reaction mixture was added dropwise to hexane to precipitate and recover the block polymer (P-7). From NMR measurements, it was confirmed that 4 HBAGE units and 3 n-butyl acrylate units were introduced into one molecule of block polymer.

[0521] 5. Preparation of solution and film production

[0522] (1) Epoxy coating

[0523] As an epoxy compound forming a matrix, cellulose 2021P (manufactured by Daicel Co., Ltd.) was dissolved in MIBK, and to the solution, PFPE block polymers (P-1), (P-2), and (P-7) synthesized in Synthesis Examples 2 and 3 were each added to the solution in an amount of 1% in terms of solid content concentration relative to the epoxy compound solid content, and silicone compounds (S-1) to (S-9) were each added in the combinations and amounts (relative to matrix-forming compounds) shown in Table 1 below in terms of solid content concentration relative to the epoxy compound solid content, thereby preparing a 50 mass% epoxy compound solution (Examples 1 to 9, 18 to 21, Comparative Examples 4 to 7). In addition, a solution containing only a silicone compound (S-2) without adding a PFPE block polymer (Comparative Example 1), and a solution containing only a PFPE block polymer (P-1) or (P-2) without adding a silicone compound (Comparative Examples 2 and 3) were also prepared. Furthermore, a coating agent was obtained by adding 3 mass% of San-Aid SI-60L (manufactured by Sanshin Kagaku Kogyo Co., Ltd.), a thermal acid generating agent, relative to the solid content of the epoxy compound. The coating agent was applied to a PET substrate using a bar coater and heated under conditions of 90°C for 2 hours to obtain a cured film.

[0524] (2) Acrylic coating

[0525] Beam set 575CB (manufactured by Arakawa Kagaku Kogyo Co., Ltd.) was dissolved in MIBK as a composition containing an acrylic compound forming a matrix, and PFPE block polymers (P-4) and (P-5) synthesized in Synthesis Examples 5 and 6 were added to the solution such that, each was 1% in terms of solid content concentration relative to the resin solid content of Beam set 575CB, and silicone compounds (S-1), (S-4), and (S-6) were added in combinations and amounts (relative to matrix-forming compounds) in terms of solid content concentration relative to the resin solid content of Beam set 575CB, as shown in Table 2 below, to obtain a coating composition of 50 mass% (Examples 10 to 17, Comparative Examples 10, 11, 13, and 14). In addition, a coating agent was prepared in which only a silicone compound (S-4) was added without adding a PFPE block polymer (Comparative Example 8), a coating agent in which only a PFPE block polymer (P-4) or (P-5) was added without adding a silicone compound (Comparative Examples 9 and 12), and a coating agent in which a PFPE compound having an acrylic group (P-6) synthesized in Comparative Synthesis Example 1 was added instead of a PFPE block polymer (Comparative Examples 15 and 16). The above-described coating compositions were applied to a PET substrate using a bar coater, dried under conditions of 70°C for 10 minutes, and then irradiated with ultraviolet light to obtain a cured film. A belt conveyor type ultraviolet irradiation device was used for ultraviolet irradiation, and the irradiation dose was set to 600 mJ / cm².

[0526] silicon compounds

[0527] S-1: FM-0411 (JNC Co., Ltd., monoterminal OH polydimethylsiloxane, number average molecular weight 1,000)

[0528] S-2: FM-0421 (JNC Co., Ltd., single-terminal OH polydimethylsiloxane, number average molecular weight 5,000)

[0529] S-3: FM-0425 (JNC Co., Ltd., monoterminal OH polydimethylsiloxane, number average molecular weight 10,000)

[0530] S-4: KF-2012 (Shin-Etsu Kagaku High School Co., Ltd., single-terminal polydimethylsiloxane methacrylate, number average molecular weight 4,600)

[0531] S-5: KF-96-2cs (Shin-Etsu Kagaku Kogyo Co., Ltd., terminally unmodified polydimethylsiloxane, number average molecular weight 350)

[0532] S-6: KF-96-100cs (Shin-Etsu Kagaku Kogyo Co., Ltd., terminally unmodified polydimethylsiloxane, number average molecular weight 6,000)

[0533] S-7: X-22-173DX (Shin-Etsu Kagaku High School Co., Ltd., single-terminal epoxy polydimethylsiloxane, number average molecular weight 4,600)

[0534] S-8: X-22-163B (Shin-Etsu Kagaku High School Co., Ltd., double-layered epoxy polydimethylsiloxane, number average molecular weight 3,600)

[0535] S-9: DMS-A15 (Gelest, double-banded amine polydimethylsiloxane, number average molecular weight 3,000)

[0536]

[0537]

[0538] <Evaluation>

[0539] For the above examples and comparative examples, compatibility, film appearance, contact angle, and surface slipperiness were evaluated as follows. The results are shown in Table 3 (epoxy-based coating) and Table 4 (acrylic-based coating) below.

[0540] 6. Commercialization Evaluation

[0541] Regarding the solution prepared in 5 above, the condition of the solution was visually inspected. The evaluation criteria were as follows.

[0542] G: It was transparent and also dissolved uniformly.

[0543] NG: Turbidity or separation of remains is confirmed.

[0544] 7. Coating appearance

[0545] The cured film prepared in 5 above was visually observed. The evaluation criteria were as follows.

[0546] G: Smooth without unevenness.

[0547] NG: Non-uniformity and cratering are observed.

[0548] 8. Contact Angle Evaluation

[0549] For the cured film prepared in 5 above, the static contact angle of water was measured using a contact angle meter (Kyowa Kaimen Kagaku Co., Ltd., “DropMaster”) with a liquid volume of 2 μL. Measurements were not performed on the film with a non-perfect appearance.

[0550] 9. Evaluation of Surface Sleekness

[0551] For the cured film prepared in 5 above, the static friction coefficient and kinetic friction coefficient were measured using a friction meter ("Tribomaster TL201Ts, manufactured by Trinity Lab Co., Ltd.") and a tactile contactor as the frictional element, with a load of 20 gf and a scanning speed of 10 mm / sec. Measurements were not performed on the film with a non-perforated appearance.

[0552]

[0553]

[0554] As described above, it has been confirmed that a composition comprising a fluoropolyether group-containing polymer (P-1 to P-5, P-7) and a siloxane polymer (S-1, S-2, S-4, S-6 to S-9) included within the scope of the present invention has high compatibility, good coating film appearance, and a large logarithmic contact angle of 113 degrees or more and high slipperiness. Industrial applicability

[0555] The surface treatment agent of the present disclosure can be suitably used to form a surface treatment layer on the surface of various substrates, particularly optical members requiring transparency.

Claims

Claim 1 (A) a surface treatment agent comprising a fluoropolyether group-containing polymer and (B) a siloxane polymer, wherein the fluoropolyether group-containing polymer is of the following formula (1) or (2): [Eating:R F1 silver, Rf 1 -R F -O q - and;R F2 is, -Rf 2 p -R F -O q -igo;Rf 1 Silver, C which may be substituted by one or more fluorine atoms 1-16 It is an alkyl group; Rf 2 C, which may be substituted by one or more fluorine atoms. 1-6 It is an alkylene group; R F is, each independently, a divalent fluoropolyether group; p is 0 or 1; q is, each independently, 0 or 1; and R 4 is, independently in each appearance, R 4a or R 4b Igo;R 4a is a divalent organic group having a bridging group, independently in each appearance; R 4b is, independently in each appearance, a divalent organic group not having a crosslinking group; said crosslinking group is a group comprising a carbon-carbon double bond, a carbon-carbon triple bond, a cyclic ether group, a hydroxyl group, a thiol group, an amino group, an azide group, a nitrogen-containing heterocyclic group, an isocyanate group, a halogen atom, a phosphate-containing group, or a silane coupling group, or a precursor group thereof; n is an integer from 1 to 100; and R 4 n Middle, R 4a The number of is 1 or greater; X a are, each independently, divalent organic groups; X b are, each independently, divalent organic groups; R a are, respectively, alkyl, phenyl, -SR a1 , -OR a2 , -NR a3 2, Igo;R a1 , R a2 , R a3 , R a4 , R a5 and R a6 Each is independently an alkyl group or a phenyl group; R a7 A surface treatment agent comprising a copolymer represented as [silver, hydrogen, or halogen atoms], wherein the number average molecular weight of the siloxane polymer is 800 to 8,000, and the content of the siloxane polymer is 1 to 300 parts by mass per 100 parts by mass of the fluoropolyether group-containing polymer. Claim 2 In paragraph 1, R F is, each independently, formula: [In the middle of the meal, R Fa A surface treatment agent represented by [where each appearance is independently a hydrogen atom, a fluorine atom, or a chlorine atom, a, b, c, d, e, and f are each independently integers from 0 to 200, the sum of a, b, c, d, e, and f is 1 or greater, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the expression.] Claim 3 In paragraph 2, R Fa is a surface treatment agent that is a fluorine atom. Claim 4 In any one of paragraphs 1 to 3, R F are, respectively, the following expressions (f1), (f2), (f3), (f4) or (f5): [In the expression, d is an integer from 1 to 200, and e is 0 or 1.], [In the expression, c and d are each independently integers from 0 to 30; e and f are each independently integers from 1 to 200; the sum of c, d, e and f is an integer from 10 to 200; and the order of existence of each repetition unit enclosed in parentheses with subscripts c, d, e, or f is arbitrary in the expression.] [In the middle of the meal, R 6 is, OCF2 or OC2F4 and;R 7 Silver, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It is a group selected from, or a combination of 2 or 3 groups selected from these groups; g is an integer from 2 to 100. [In the expression, e is an integer between 1 and 200 inclusive, a, b, c, d, and f are each independently integers between 0 and 200 inclusive, and the order of existence of each repetition unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the expression.] A surface treatment agent represented by [wherein f is an integer between 1 and 200 inclusive, a, b, c, d, and e are each independently integers between 0 and 200 inclusive, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary within the expression.] Claim 5 In any one of paragraphs 1 to 3, R 4 is, R 4a Phosphorus, surface treatment agent. Claim 6 In any one of paragraphs 1 to 3, R 4a is, the following formula: [Eating:R 31 Silver, independently in each appearance, is a hydrogen atom or an alkyl group; R 32 is an alkyl group that may be substituted by a hydrogen atom, a chlorine atom, a fluorine atom, or fluorine, independently in each appearance; R 33 is, independently in each appearance, a bridging group; Y 1 silver, single bond, -C(=O)O-, -C(=O)NH-, -OC(=O)-, -NHC(=O)-, -O-, -N(R c )-, aromatic ring, aromatic ring having a substituent or carbazolylene;R c is an organic group, and Y 2 A surface treatment agent characterized by being a linker having 1 to 16 atoms of a single bond or main chain. Claim 7 A surface treatment agent according to any one of claims 1 to 3, wherein the crosslinking group is an epoxy group, a glycidyl group, a dicyclic epoxy group, a vinyl group, an allyl group, an acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group, a vinyl ether group, a hydroxyl group, an oxetanyl group, an isocyanate group, a catechol group, a thiol group, an amino group, an alkylamino group, a dialkylamino group, an azide group, a phosphate-containing group, a carboxyl group, an imidazolyl group, a triazolyl group, a benzotriazolyl group, a tetrazolyl group, a halogen atom, or a silane coupling group, or a precursor group thereof. Claim 8 A surface treatment agent according to any one of claims 1 to 3, wherein the crosslinking group is an epoxy group, a glycidyl group, a cycloaliphatic epoxy group, an acryloyl group, or a methacryloyl group. Claim 9 A surface treatment agent according to any one of claims 1 to 3, wherein n is an integer from 2 to 50. Claim 10 In any one of claims 1 to 3, the siloxane polymer is of the following formula: [Eating:R 21 Silver, independently in each appearance, hydrogen atom, C 1-6 It is an alkyl group or an aryl group, and R 22 is, independently in each appearance, a hydrogen atom, C 1-6 It is an alkyl group or an aryl group, and R 23 Silver, hydrogen atom, C 1-6 It is an alkyl group or an aryl group, and R 24 is, hydrogen atom, C 1-6 It is an alkyl group or an aryl group, and R 25 is a hydrogen atom or a monovalent organic group, and R 26 A surface treatment agent, which is a siloxane polymer represented as [siloxane is a hydrogen atom or a monovalent organic group, and p is any integer.] Claim 11 In Paragraph 10, R 25 and R 26 silver, C 1-6 Alkyl group, surface treatment agent. Claim 12 In Paragraph 10, R 25 is C 1-6 It is an alkyl group, and R 26 silver, -R 27 -R 28 and, R 27 Silver, a divalent organic group, an oxygen atom, or a single bond, and R 28 A surface treatment agent that is silver, a hydrogen atom, -OH, -CO-CH=CH2, -CO-C(CH3)=CH2, an epoxy group, alicyclic epoxy group, an amino group, a carboxyl group, a vinyl group, an alkoxy group, or a thiol group. Claim 13 In Paragraph 10, R 25 and R 26 silver, -R 27 -R 28 and, R 27 Silver, a divalent organic group, an oxygen atom, or a single bond, and R 28 A surface treatment agent that is silver, a hydrogen atom, -OH, -CO-CH=CH2, -CO-C(CH3)=CH2, an epoxy group, alicyclic epoxy group, an amino group, a carboxyl group, a vinyl group, an alkoxy group, or a thiol group. Claim 14 delete Claim 15 delete Claim 16 delete Claim 17 delete Claim 18 delete Claim 19 delete Claim 20 delete Claim 21 delete Claim 22 delete Claim 23 delete Claim 24 delete Claim 25 delete

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