Fluoropolyether group-containing compound

Abstract

To provide a fluorine-containing compound having excellent solubility in a solvent.SOLUTION: There is provided a fluorine-containing compound represented by the following formula (1) [wherein, R1 is a divalent cyclic group, RA each independently is a group containing -OCO-CR3=CH2, R3 each independently is a hydrogen atom or a hydrocarbon group, RB is a monovalent or divalent group containing a fluoropolyether group, RC each independently is a hydrogen atom or a monovalent group and α is 1 or 2.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to fluoropolyether group-containing compounds. [Background technology]

[0002] It is known that certain fluorine-containing compounds, when used for surface treatment of substrates, can provide excellent water repellency, oil repellency, antifouling properties, etc. Layers obtained from surface treatment agents containing fluorine-containing compounds (hereinafter also referred to as "surface treatment layers") are applied as so-called functional thin films to a wide variety of substrates, such as glass, plastics, fibers, and building materials (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-160902 Summary of the Invention [Problem to be solved by the invention]

[0004] The object of the present invention is to provide a fluorine-containing compound having excellent solubility in solvents. [Means for solving the problem]

[0005] The present disclosure includes the following aspects. [1] The following formula (1): [ka] [In formula: R 1 is a divalent cyclic group, R A are each independently -OCO-CR 3 is a group containing =CH2, R 3 are each independently a hydrogen atom or a hydrocarbon group, R Bis a monovalent or divalent group containing a fluoropolyether group, R C are each independently a hydrogen atom or a monovalent group, α is 1 or 2. A fluorine-containing compound represented by the formula: [2] R 1 is a divalent cyclic group containing N, S, or O. [3] R 1 is a nitrogen-containing ring. [4] R 1 The fluorine-containing compound according to any one of the above [1] to [3], wherein is a 5- to 8-membered ring. [5] R 1 The fluorine-containing compound according to any one of the above [1] to [4], wherein is 1,4-piperazinediyl. [6] R A are each independently -X A1 (-X A2 (R Ac ) A2 ) A1 and X A1 represents a single bond or a divalent to pentavalent organic group, X A2 are each independently a single bond or a divalent or trivalent organic group, A1 is X A1 is the valence of -1, A2 is X A2 is the valence of -1, R Ac are each independently -OCO-CR 3 =CH2, R 3 are each independently a hydrogen atom or a hydrocarbon group; The fluorine-containing compound according to any one of the above [1] to [5]. [7] X A1 The fluorine-containing compound according to the above [6], wherein is a single bond. [8] X A1 The divalent to pentavalent organic group inA11 -R A12 - or -R A13 (-R A12 )2, R A11 is C 1-20 Alkylene group, -(CH2) z1 -O-(CH2) z2 - (wherein z1 is an integer of 0 to 10, and z2 is an integer of 0 to 10), or -(CH2) z3 -phenylene-(CH2) z4 - (wherein z3 is an integer of 0 to 10, and z4 is an integer of 0 to 10), R A12 is -O-, -CO-, or -NR 11 - and R 11 is a hydrogen atom or a hydrocarbon group, R A13 is a trivalent C 1-10 Hydrocarbon group or trivalent C 1-10 A group containing one or more O in the main chain of a hydrocarbon group. The fluorine-containing compound according to [6] above. [9] X A2 is -CO-NH-C(R 13 )(R 14 )2, R 13 is a hydrogen atom or C 1-6 is an alkyl group, R 14 are each independently 1-6 is an alkylene group, The fluorine-containing compound according to any one of the above items [6] to [8].

[10] R B -X B1 -R F1 , or -X B1 -R F2 -X B1 - and R F1 is a monovalent fluoropolyether group, R F2 is a divalent fluoropolyether group, X B1are each independently a single bond or a divalent organic group; The fluorine-containing compound according to any one of the above items [1] to [9].

[11] R F1 is Rf 1 -R F -O q - and R F2 is -Rf 2 p -R F -O q - and Rf 1 C optionally substituted with one or more fluorine atoms 1-16 is an alkyl group, Rf 2 C optionally substituted with one or more fluorine atoms 1-6 is an alkylene group, R F are each independently a divalent fluoropolyether group, p is 0 or 1; Each q is independently 0 or 1; The fluorine-containing compound according to

[10] above.

[12] R F are each independently of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [In formula: R Fa are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, a, b, c, d, e, and f each independently represent an integer of 0 to 200, the sum of a, b, c, d, e, and f is 1 or more, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] The fluorine-containing compound according to the above

[11] , wherein the group is represented by the following formula:

[13] R Fa is a fluorine atom.

[14] R F are each independently represented by the following formula (f1), (f2), (f3), (f4), (f5) or (f6): -(OC3F6) d -(OC2F4) e - (f1) [wherein d is an integer of 1 to 200, and e is 0 or 1.] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d each independently represent an integer of 0 to 30; e and f each independently represent an integer of 1 to 200; The sum of c, d, e, and f is an integer of 10 to 200; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula. -(R 6 -R 7 ) g -R 9 - (f3) [In the formula, R 6 is OCF2 or OC2F4; R 7 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups selected from these groups; R 9 is a single bond or OCF2, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups selected from these groups; g is an integer from 2 to 100. -(R 6 -R 7 ) g -R r -(R 7’ -R 6’ ) g’ - (f4) [In the formula, R 6 is OCF2 or OC2F4, R 7 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, R 6’ is OCF2 or OC2F4, R 7’ are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100, g' is an integer from 2 to 100, R r teeth, [ka] (In the formula, * indicates the bonding position.) ]; -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) [In the formula, e is an integer of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] -(OC6F 12 ) a-(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f6) [In the formula, f is an integer of 1 or more and 200 or less, a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] The fluorine-containing compound according to the above

[11] , wherein the group is represented by the following formula:

[15] Rf 1 are each independently 1-16 is a perfluoroalkyl group, Rf 2 are each independently 1-6 is a perfluoroalkylene group, The fluorine-containing compound according to any one of the above

[11] to

[14] .

[16] X B1 are each independently represented by the following formula: -(CX 121 X 122 ) b1 -(X B1a ) b2 -(CX 123 X 124 ) b3 - [In the formula, X 121 ~X 124 are independently H, C 1-6 an alkyl group or a halogen; X B1a is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, or -NHC(=O)NH-, b1 is an integer of 0 to 10, b2 is 0 or 1, b3 is an integer of 0 to 10, and the sum of b1, b2, and b3 is at least 1. The fluorine-containing compound according to any one of the above

[10] to

[15] , wherein the fluorine-containing compound is a group represented by the following formula:

[17] X B1 are each independently -O-(CH2) m11 - and m11 is an integer from 1 to 6. The fluorine-containing compound according to any one of the above items

[10] to

[16] .

[18] The fluorine-containing compound according to any one of the above [1] to

[16] , wherein α is 1.

[19] R C -R 1 -R A The fluorine-containing compound according to any one of the above [1] to

[18] , wherein

[20] A surface treatment agent comprising one or more compounds according to any one of the above [1] to

[19] .

[21] The surface treatment agent according to the above

[20] , which is used as an antifouling coating agent or a waterproof coating agent.

[22] An article comprising a substrate and a layer formed on the surface of the substrate using the surface treatment agent according to

[20] or

[21] above.

[23] The article according to

[22] above, wherein the article is an optical element. [Effects of the Invention]

[0006] According to the present disclosure, a fluorine-containing compound having excellent solubility in a solvent can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0007] As used herein, the term "organic group" refers to a monovalent group containing carbon. Unless otherwise specified, the monovalent organic group may be a hydrocarbon group or a derivative thereof. A hydrocarbon group derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, sulfoxide, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain. Furthermore, the term "divalent organic group" refers to a divalent group containing carbon. Such divalent organic groups are not particularly limited, but include divalent groups in which one hydrogen atom has been further eliminated from an organic group.

[0008] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is a hydrocarbon group from which one hydrogen atom has been removed. Such hydrocarbon groups include, but are not limited to, C 1-20 Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The hydrocarbon group may be substituted with one or more substituents. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures.

[0009] As used herein, the substituent of the "hydrocarbon group" is not particularly limited, but examples thereof include a halogen atom, a C 1-6 Alkyl group, C 2-6 Alkenyl group, C 2-6 Alkynyl group, C 3-10 Cycloalkyl groups, C 3-10 Unsaturated cycloalkyl groups, 5-10 membered heterocyclyl groups, 5-10 membered unsaturated heterocyclyl groups, C 6-10 Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0010] The fluorine-containing compound of the present disclosure will be described below.

[0011] The present disclosure provides a compound of formula (1): [ka] [In formula: R 1 is a divalent cyclic group, R A are each independently -OCO-CR 3 is a group containing =CH2, R 3 are each independently a hydrogen atom or a hydrocarbon group, R Bis a monovalent or divalent group containing a fluoropolyether group, R C are each independently a hydrogen atom or a monovalent group, α is 1 or 2. The present invention provides a fluorine-containing compound represented by the formula:

[0012] R 1 is a divalent cyclic group. 1 When is a cyclic group, the solubility of the fluorine-containing compound represented by formula (1) is improved.

[0013] In one embodiment, R 1 is a divalent cyclic group containing N, S, or O, and is preferably a nitrogen-containing ring. 1 When is a divalent cyclic group containing N, S or O, particularly a nitrogen-containing ring, the solubility of the fluorine-containing compound represented by formula (1) is further improved.

[0014] R 1 In the cyclic group, the number of N, S, and O may be, for example, 1 to 6, preferably 1 to 4, more preferably 2 to 4, and even more preferably 2 or 3.

[0015] R 1 The cyclic group may be monocyclic or polycyclic.

[0016] In one embodiment, R 1 is a 5- to 8-membered ring, preferably a 5- or 6-membered ring.

[0017] In a preferred embodiment, R 1 is a 5- to 8-membered nitrogen-containing ring, preferably a 5- or 6-membered nitrogen-containing ring.

[0018] R 1 is preferably 1,4-piperazinediyl.

[0019] R A are each independently -OCO-CR 3 =CH2-containing group. 3are each independently a hydrogen atom or a hydrocarbon group.

[0020] The hydrocarbon group is preferably C 1-6 It is an alkyl group. 1-6 The alkyl group may be straight-chain or branched, preferably straight-chain. 1-6 The alkyl group is preferably C 1-4 It is an alkyl group, more preferably a methyl group.

[0021] In one embodiment, R 3 is a hydrogen atom.

[0022] In another embodiment, R 3 is a hydrocarbon group, preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0023] In one embodiment, R A are each independently -X A1 (-X A2 (R Ac ) A2 ) A1 is.

[0024] X A1 represents a single bond or a divalent to pentavalent organic group. A1 The valence of is -1.

[0025] In one embodiment, X A1 is a single bond.

[0026] In one embodiment, X A1 is a divalent to pentavalent organic group.

[0027] The divalent to pentavalent organic group is preferably -R A11 -R A12 - or -R A13 (-R A12 )2.

[0028] In one embodiment, the divalent to pentavalent organic group is -R A11 -RA12 -It is.

[0029] In another embodiment, the divalent to pentavalent organic group is —R A13 (-R A12 )2.

[0030] R A11 is C 1-20 Alkylene group, -(CH2) z1 -O-(CH2) z2 - (wherein z1 is an integer of 0 to 10, preferably an integer of 0 to 6, and z2 is an integer of 0 to 10, preferably an integer of 0 to 6), or -(CH2) z3 -phenylene-(CH2) z4 - (wherein z3 is an integer of 0 to 10, preferably an integer of 0 to 6, and z4 is an integer of 0 to 10, preferably an integer of 0 to 6).

[0031] Above C 1-20 The alkylene group may be a straight chain or a branched chain, and is preferably a straight chain. 1-20 The alkylene group is preferably C 2-16 Alkylene groups, such as C 4-16 Alkylene group, C 4-12 Alkylene group, C 6-12 Alkylene group, or C 6-10 It may be an alkylene group.

[0032] R A12 is -O-, -CO-, or -NR 11 -R A12 is preferably —O—.

[0033] R 11 is a hydrogen atom or a hydrocarbon group. The hydrocarbon group is preferably C 1-6 It is an alkyl group. 1-6 The alkyl group may be straight-chain or branched, preferably straight-chain. 1-6 The alkyl group is preferably C 1-4 It is an alkyl group, more preferably a methyl group.

[0034] R A13 is a trivalent C 1-10 Hydrocarbon group or trivalent C 1-10 A group containing one or more O in the main chain of a hydrocarbon group. 1-10 The hydrocarbon group containing one or more oxygen atoms in the main chain is C 1-10 It is a group containing O at the end of a hydrocarbon group or between carbon atoms in the main chain.

[0035] The above trivalent C 1-10 The hydrocarbon group may be linear, branched, or cyclic, but is preferably branched. 1-10 The hydrocarbon group is preferably C 3-10 Hydrocarbon groups, more preferably C 3-8 It is a hydrocarbon group.

[0036] R A13 is preferably C 1-10 It is a hydrocarbon group.

[0037] X A2 are each independently a divalent or trivalent organic group. A2 is X A2 The valence of is -1.

[0038] X A2 is preferably —CO—NH—C(R 13 )(R 14 )2.

[0039] R 13 is a hydrogen atom or C 1-6 The above C is an alkyl group. 1-6 The alkyl group may be straight-chain or branched, preferably straight-chain. 1-6 The alkyl group is preferably C 1-4 It is an alkyl group, more preferably a methyl group.

[0040] R 14 are each independently 1-6 It is an alkylene group. 1-6 The alkylene group may be a straight chain or a branched chain, and is preferably a straight chain.1-6 The alkylene group is preferably C 1-4 It is an alkylene group, and more preferably a methylene group.

[0041] R Ac are each independently -OCO-CR 3 =CH2, and R 3 are as defined above, and each independently represents a hydrogen atom or a hydrocarbon group.

[0042] R B R is a monovalent or divalent group containing a fluoropolyether group. B is preferably -X B1 -R F1 , or -X B1 -R F2 -X B1 -It is.

[0043] R F1 is a monovalent fluoropolyether group, preferably Rf 1 -R F -O q -It is.

[0044] R F2 is a divalent fluoropolyether group, preferably -Rf 2 p -R F -O q -It is.

[0045] Rf 1 C optionally substituted with one or more fluorine atoms 1-16 It is an alkyl group.

[0046] C optionally substituted with one or more fluorine atoms 1-16 "C" in alkyl group 1-16 The "alkyl group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-6 Alkyl groups, especially C 1-3 alkyl group, more preferably a straight-chain C 1-6 Alkyl groups, especially C 1-3It is an alkyl group.

[0047] Rf 1 is preferably C substituted by one or more fluorine atoms 1-16 alkyl group, more preferably CF2H-C 1-15 perfluoroalkylene groups, more preferably C 1-16 It is a perfluoroalkyl group.

[0048] Above C 1-16 The perfluoroalkyl group may be linear or branched, and is preferably a linear or branched C 1-6 Perfluoroalkyl groups, especially C 1-3 perfluoroalkyl groups, more preferably linear C 1-6 Perfluoroalkyl groups, especially C 1-3 A perfluoroalkyl group, specifically -CF3, -CF2CF3, or CF2CF2CF3.

[0049] Rf 2 C optionally substituted with one or more fluorine atoms 1-6 It is an alkylene group.

[0050] C optionally substituted with one or more fluorine atoms 1-6 "C" in the alkylene group 1-6 The "alkylene group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-3 It is preferably a linear alkylene group. 1-3 It is an alkylene group.

[0051] Rf 2 is preferably C substituted by one or more fluorine atoms 1-6 is an alkylene group, more preferably C 1-6 A perfluoroalkylene group, more preferably C 1-3 It is a perfluoroalkylene group.

[0052] Above C1-6 The perfluoroalkylene group may be a straight chain or a branched chain, and is preferably a straight chain or branched C 1-3 A perfluoroalkylene group, more preferably a linear C 1-3 A perfluoroalkylene group, specifically, -CF2-, -CF2CF2-, or CF2CF2CF2-.

[0053] In the above formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0054] q is 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.

[0055] R F are each independently a divalent fluoropolyether group.

[0056] R F is preferably: -(OC h1 R Fa 2h1 ) h3 -(OC h2 R Fa 2h2-2 ) h4 - [In formula: R Fa are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, h1 is an integer from 1 to 6, h2 is an integer from 4 to 8, h3 is an integer equal to or greater than 0, h4 is an integer equal to or greater than 0, However, the number of repeating units of h3 and h4 is 1 or more, preferably 2 or more, and more preferably 5 or more, and the order of the repeating units enclosed in parentheses with h3 and h4 is arbitrary in the formula.] It may contain a group represented by:

[0057] In one embodiment, R F R can be linear or branched.F is preferably of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [In formula: R Fa are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, a, b, c, d, e, and f each independently represent an integer of 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more. The order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] It is a group represented by the following formula:

[0058] R Fa is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom.

[0059] Preferably, a, b, c, d, e and f may each independently be an integer of 0 to 100.

[0060] 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, and even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0061] These repeating units may be linear or branched. For example, the repeating unit may be -(OCF 12)- may be -(OCF2CF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. 10 )- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and (OCF2CF(C2F5))-. -(OC3F6)- (i.e., in the above formula, R Fa is a fluorine atom) may be any of -(OCFCFCF)-, -(OCF(CF)CF)-, and (OCFCF(CF))-. -(OCF)- may be any of -(OCFCF)- and (OCF(CF))-.

[0062] In one embodiment, the repeating unit is linear. By making the repeating unit linear, the surface smoothness, friction durability, etc. of the surface treatment layer can be improved.

[0063] In one embodiment, the repeating unit is branched. By making the repeating unit branched, the dynamic friction coefficient of the surface treatment layer can be increased.

[0064] In one embodiment, R F may contain a ring structure.

[0065] The ring structure may be a three-, four-, five-, or six-membered ring as shown below. [ka] [In the formula, * indicates the bonding position.]

[0066] The ring structure may be preferably a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.

[0067] The repeating unit having a ring structure may preferably be the following unit. [ka] [In the formula, * indicates the bonding position.]

[0068] In one embodiment, R F are each independently a group represented by any one of the following formulas (f1) to (f6). -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer of 1 to 200, and e is 0 or 1.] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d each independently represent an integer of 0 or more and 30 or less, and e and f each independently represent an integer of 1 or more and 200 or less, the sum of c, d, e, and f is 2 or more; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula.]; -(R 6 -R 7 ) g -R 9 - (f3) [In the formula, R 6 is OCF2 or OC2F4, R 7are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, R 9 is a single bond or OCF2, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups selected from these groups; g is an integer from 2 to 100; -(R 6 -R 7 ) g -R r -(R 7’ -R 6’ ) g’ - (f4) [In the formula, R 6 is OCF2 or OC2F4, R 7 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, R 6’ is OCF2 or OC2F4, R 7’ are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100, g' is an integer from 2 to 100, R r teeth, [ka] (In the formula, * indicates the bonding position.) ]; -(OC6F 12 ) a-(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) [In the formula, e is an integer of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f6) [In the formula, f is an integer of 1 or more and 200 or less, a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.]

[0069] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, even more preferably 15 to 50, for example, an integer of 25 to 35. In one embodiment, e is 1. In another embodiment, e is 0. In the above formula (f1), (OC3F6) is preferably a group represented by (OCF2CF2CF2), (OCF2CF(CF3)) or (OCF(CF3)CF2), and more preferably -(OCF2CF2CF2) d In the above formula (f1), (OC2F4) is a group represented by (OCF2CF2) or (OCF(CF3)), and preferably a group represented by (OCF2CF2).

[0070] In the formula (f2), e and f are each independently an integer of preferably 5 or more and 200 or less, more preferably 10 to 200. 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 formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f In another embodiment, formula (f2) is a group represented by -(OC2F4) e -(OCF2) f It may also be a group represented by the formula -.

[0071] In the above formula (f3), R 6 is preferably OC2F4. In the above (f3), R 7 is preferably a group selected from OC2F4, OC3F6 and OC4F8, or a combination of two or three groups independently selected from these groups, more preferably a group selected from OC3F6 and OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8 is not particularly limited, and examples thereof include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC Examples include 2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-, and OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F12 may be either a straight chain or a branched chain, and is preferably a straight chain. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g -or (OC2F4-OC4F8) g In one embodiment, R 9 is a single bond. 9 are OCF2, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups selected from these groups. 9 is preferably a group selected from OCF2, OC2F4, OC3F6, and OC4F8, or a combination of two or three groups selected from these groups, and more preferably -OC2F4OC3F6-.

[0072] In the above formula (f4), R 6 , R 7 and g have the same meanings as those in the formula (f3) above, and have the same embodiments. 6’ , R 7’ and g' are R 6 , R 7 and g have the same meaning and similar aspects. r is preferably [ka] [In the formula, * indicates the bonding position.] and more preferably [ka] [In the formula, * indicates the bonding position.] is.

[0073] In the above formula (f5), e is preferably an integer of 1 or more and 100 or less, more preferably an integer 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.

[0074] In the above formula (f6), f is preferably an integer of 1 or more and 100 or less, more preferably 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.

[0075] In one embodiment, R F is a group represented by the above formula (f1).

[0076] In one embodiment, R F is a group represented by the above formula (f2).

[0077] In one embodiment, R F is a group represented by the above formula (f3).

[0078] In one embodiment, R F is a group represented by the above formula (f4).

[0079] In one embodiment, R F is a group represented by the above formula (f5).

[0080] In one embodiment, R F is a group represented by the above formula (f6).

[0081] R F In the formula, the ratio of e to f (hereinafter referred to as "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 setting the e / f ratio to 10 or less, the slipperiness, friction 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 improved the slipperiness and friction durability of the surface treatment layer. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further improved. The higher the e / f ratio, the more improved the stability of the compound.

[0082] In one embodiment, the e / f ratio is preferably 0.2 to 0.95, and more preferably 0.2 to 0.9.

[0083] In one embodiment, from the viewpoint of heat resistance, the e / f ratio is preferably 1.0 or more, and more preferably 1.0 to 2.0.

[0084] In the above fluoropolyether group-containing compound, R F1 and R F2 The number average molecular weight of R is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. F1 and R F2 The number average molecular weight of 19 The value is measured by F-NMR.

[0085] In another embodiment, R F1 and R F2 The number average molecular weight of the copolymer 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.

[0086] In another embodiment, R F1 and R F2 The number average molecular weight of the copolymer may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0087] In the above formula, Rf 1 C optionally substituted with one or more fluorine atoms 1-16 It is an alkyl group.

[0088] C optionally substituted with one or more fluorine atoms 1-16 "C" in alkyl group 1-16 The "alkyl group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C1-6 Alkyl groups, especially C 1-3 alkyl group, more preferably a straight-chain C 1-6 Alkyl groups, especially C 1-3 It is an alkyl group.

[0089] Above Rf 1 is preferably C substituted by one or more fluorine atoms 1-16 alkyl group, more preferably CF2H-C 1-15 perfluoroalkylene groups, more preferably C 1-16 It is a perfluoroalkyl group.

[0090] Above C 1-16 The perfluoroalkyl group may be linear or branched, and is preferably a linear or branched C 1-6 Perfluoroalkyl groups, especially C 1-3 perfluoroalkyl groups, more preferably linear C 1-6 Perfluoroalkyl groups, especially C 1-3 A perfluoroalkyl group, specifically -CF3, -CF2CF3, or CF2CF2CF3.

[0091] In the above formula, Rf 2 C optionally substituted with one or more fluorine atoms 1-6 It is an alkylene group.

[0092] C optionally substituted with one or more fluorine atoms 1-6 "C" in the alkylene group 1-6 The "alkylene group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-3 It is preferably a linear alkylene group. 1-3 It is an alkylene group.

[0093] Above Rf 2 is preferably C substituted by one or more fluorine atoms 1-6 is an alkylene group, more preferably C 1-6A perfluoroalkylene group, more preferably C 1-3 It is a perfluoroalkylene group.

[0094] Above C 1-6 The perfluoroalkylene group may be a straight chain or a branched chain, and is preferably a straight chain or branched C 1-3 A perfluoroalkylene group, more preferably a linear C 1-3 A perfluoroalkylene group, specifically, -CF2-, -CF2CF2-, or CF2CF2CF2-.

[0095] In the above formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0096] In the above formula, q is 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.

[0097] In the above formulas (1) and (2), R F are each independently a divalent fluoropolyether group.

[0098] R F is preferably: -(OC h1 R Fa 2h1 ) h3 -(OC h2 R Fa 2h2-2 ) h4 - [In formula: R Fa are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, h1 is an integer from 1 to 6, h2 is an integer from 4 to 8, h3 is an integer equal to or greater than 0, h4 is an integer equal to or greater than 0, However, the number of repeating units of h3 and h4 is 1 or more, preferably 2 or more, and more preferably 5 or more, and the order of the repeating units enclosed in parentheses with h3 and h4 is arbitrary in the formula.] It may contain a group represented by:

[0099] In one embodiment, R F R can be linear or branched. F is preferably of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [In formula: R Fa are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, a, b, c, d, e, and f each independently represent an integer of 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more. The order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] It is a group represented by the following formula:

[0100] R Fa is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom.

[0101] Preferably, a, b, c, d, e and f may each independently be an integer of 0 to 100.

[0102] 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, and even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0103] These repeating units may be linear or branched. For example, the repeating unit may be -(OCF 12 )- may be -(OCF2CF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. 10 )- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and (OCF2CF(C2F5))-. -(OC3F6)- (i.e., in the above formula, R Fa is a fluorine atom) may be any of -(OCFCFCF)-, -(OCF(CF)CF)-, and (OCFCF(CF))-. -(OCF)- may be any of -(OCFCF)- and (OCF(CF))-.

[0104] In one embodiment, the repeating unit is linear. By making the repeating unit linear, the surface smoothness, friction durability, etc. of the surface treatment layer can be improved.

[0105] In one embodiment, the repeating unit is branched. By making the repeating unit branched, the dynamic friction coefficient of the surface treatment layer can be increased.

[0106] In one embodiment, R Fmay contain a ring structure.

[0107] The ring structure may be a three-, four-, five-, or six-membered ring as shown below. [ka] [In the formula, * indicates the bonding position.]

[0108] The ring structure may be preferably a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.

[0109] The repeating unit having a ring structure may preferably be the following unit. [ka] [In the formula, * indicates the bonding position.]

[0110] In one embodiment, R F are each independently a group represented by any one of the following formulas (f1) to (f6). -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer of 1 to 200, and e is 0 or 1.] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d each independently represent an integer of 0 or more and 30 or less, and e and f each independently represent an integer of 1 or more and 200 or less, the sum of c, d, e, and f is 2 or more; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula.]; -(R 6 -R 7 ) g - (f3) [In the formula, R 6 is OCF2 or OC2F4, R 7 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100; -(R 6 -R 7 ) g -R r -(R 7’ -R 6’ ) g’ - (f4) [In the formula, R 6 is OCF2 or OC2F4, R 7 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, R 6’ is OCF2 or OC2F4, R 7’ are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100, g' is an integer from 2 to 100, R r teeth, [ka] (In the formula, * indicates the bonding position.) ]; -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f- (f5) [In the formula, e is an integer of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f6) [In the formula, f is an integer of 1 or more and 200 or less, a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.]

[0111] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, even more preferably 15 to 50, for example, an integer of 25 to 35. In one embodiment, e is 1. In another embodiment, e is 0. In the above formula (f1), (OC3F6) is preferably a group represented by (OCF2CF2CF2), (OCF2CF(CF3)) or (OCF(CF3)CF2), and more preferably -(OCF2CF2CF2) d In the above formula (f1), (OC2F4) is a group represented by (OCF2CF2) or (OCF(CF3)), and preferably a group represented by (OCF2CF2).

[0112] In the formula (f2), e and f are each independently an integer of preferably 5 or more and 200 or less, more preferably 10 to 200. 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 formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d-(OCF2CF2) e -(OCF2) f In another embodiment, formula (f2) is a group represented by -(OC2F4) e -(OCF2) f It may also be a group represented by the formula -.

[0113] In the above formula (f3), R 6 is preferably OC2F4. In the above (f3), R 7 is preferably a group selected from OC2F4, OC3F6 and OC4F8, or a combination of two or three groups independently selected from these groups, more preferably a group selected from OC3F6 and OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8 is not particularly limited, and examples thereof include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC Examples include 2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-, and OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 may be either a straight chain or a branched chain, and is preferably a straight chain. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g -or (OC2F4-OC4F8) g -It is.

[0114] In the above formula (f4), R 6 , R 7and g have the same meanings as those in the formula (f3) above, and have the same embodiments. 6’ , R 7’ and g' are R 6 , R 7 and g have the same meaning and similar aspects. r is preferably [ka] [In the formula, * indicates the bonding position.] and more preferably [ka] [In the formula, * indicates the bonding position.] is.

[0115] In the above formula (f5), e is preferably an integer of 1 or more and 100 or less, more preferably an integer 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.

[0116] In the above formula (f6), f is preferably an integer of 1 or more and 100 or less, more preferably 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.

[0117] In one embodiment, the R F is a group represented by the above formula (f1).

[0118] In one embodiment, the R F is a group represented by the above formula (f2).

[0119] In one embodiment, the R F is a group represented by the above formula (f3).

[0120] In one embodiment, the R F is a group represented by the above formula (f4).

[0121] In one embodiment, the R F is a group represented by the above formula (f5).

[0122] In one embodiment, the R F is a group represented by the above formula (f6).

[0123] Above R F In the formula, the ratio of e to f (hereinafter referred to as "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 setting the e / f ratio to 10 or less, the slipperiness, friction 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 improved the slipperiness and friction durability of the surface treatment layer. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further improved. The higher the e / f ratio, the more improved the stability of the compound.

[0124] In one embodiment, the e / f ratio is preferably 0.2 to 0.95, and more preferably 0.2 to 0.9.

[0125] In one embodiment, from the viewpoint of heat resistance, the e / f ratio is preferably 1.0 or more, and more preferably 1.0 to 2.0.

[0126] In the above fluoropolyether group-containing compound, R F1 and R F2 The number average molecular weight of R is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. F1 and R F2 The number average molecular weight of 19 The value is measured by F-NMR.

[0127] In another embodiment, RF1 and R F2 The number average molecular weight of the copolymer 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.

[0128] In another embodiment, R F1 and R F2 The number average molecular weight of the copolymer may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0129] X B1 are each independently a single bond or a divalent organic group.

[0130] In one embodiment, X B1 is a single bond.

[0131] In another embodiment, X B1 are each independently a divalent organic group.

[0132] In a preferred embodiment, X B1 are each independently represented by the following formula: -(CX 121 X 122 ) b1 -(X B1a ) b2 -(CX 123 X 124 ) b3 - [In the formula, X 121 ~X 124 are independently H, C 1-6 an alkyl group or a halogen; X B1a is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, or -NHC(=O)NH- (the left side of each bond is CX 121 X 122 ), b1 is an integer of 0 to 10, b2 is 0 or 1, b3 is an integer of 0 to 10, and the sum of b1, b2, and b3 is at least 1. It is a group represented by the following formula:

[0133] X B1a is preferably —O— or C(═O)O—, more preferably —O—.

[0134] X B1a is preferably of the formula: -O-(CH2) m11 - (In the formula, m11 is an integer of 1 to 6, preferably an integer of 1 to 3.) -(CH2) m12 -O-(CH2) m13 - (In the formula, m12 is an integer of 1 to 6, preferably an integer of 1 to 3, and m13 is an integer of 1 to 6, preferably an integer of 1 to 3.) It is a group represented by the following formula:

[0135] X B1a Although not particularly limited, specific examples include: Examples include -CH2-, -C2H4-, -C3H6-, -C4H8-, -O-CH2-, -O-C2H4-, and -O-C3H6-.

[0136] R C are each independently a hydrogen atom or a monovalent group.

[0137] In one embodiment, R C is a hydrogen atom.

[0138] In another embodiment, R C is a monovalent group.

[0139] The monovalent group is preferably a halogen atom, -R 1 -R A or a monovalent group containing a fluoropolyether group. Such a monovalent group containing a fluoropolyether group is R BIt has the same meaning as the monovalent group containing a fluoropolyether group in the above formula.

[0140] The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a chlorine atom or a bromine atom, and even more preferably a chlorine atom.

[0141] In a preferred embodiment, R C -R 1 -R A is.

[0142] In another preferred embodiment, R C is a halogen atom, preferably a chlorine atom.

[0143] α is 1 or 2, preferably 1.

[0144] The fluorine-containing compound of the present disclosure can be synthesized, for example, as follows.

[0145] The following formula (a): R F1 -R 51 -OH(a) [In formula: R R1 is a monovalent fluoropolyether group, R 51 is a divalent organic group. and a compound represented by the following formula (b): [ka] and a compound represented by formula (c): [ka] [In the formula, R F1 and R 51 has the same meaning as above.] The compound represented by formula (c) is mixed with a compound represented by formula (d): HR 1 -RP (d) [In the formula, R 1 is a divalent cyclic group, such as 1,4-piperazinediyl; R P is a protecting group, for example, a tert-butoxycarbonyl group (Boc). and a compound represented by formula (e): [ka] [In the formula, R F1 , R 1 , R 51 and R P has the same meaning as above.] The resulting compound represented by formula (e) is deprotected using an acid, for example, hydrochloric acid, to obtain a compound represented by formula (f): [ka] [In the formula, R F1 , R 1 , and R 51 has the same meaning as above.] The compound represented by formula (f) is reacted with a compound represented by formula (g1): OCN-R 53 -O-CO-CR 3 =CH2(g1) [In formula: R 53 is a divalent organic group, R 3 is a hydrogen atom or a hydrocarbon group. to react a compound represented by formula (h1): [ka] [In the formula, R F1 , R 1 , R 3 , R 51 and R 53 has the same meaning as above.] The fluorine-containing compound of the present disclosure represented by the formula:

[0146] Alternatively, instead of the compound represented by formula (g1) above, a compound represented by formula (g2): OCN-R 54 (O-CO-CR 3 =CH2)2(g2) [In formula: R 54 is a trivalent organic group, R 3 is a hydrogen atom or a hydrocarbon group. with a compound represented by formula (f) to obtain a compound represented by formula (h2): [ka] [In the formula, R F1 , R 51 , R 52 and R 54 has the same meaning as above.] The fluorine-containing compound of the present disclosure represented by the formula:

[0147] Next, the surface treatment agent of the present disclosure will be described.

[0148] The surface treatment agent of the present disclosure contains a fluorine-containing compound represented by formula (1).

[0149] In one embodiment, the fluorine-containing compound in the surface treatment agent of the present disclosure is a compound represented by formula (1) in which α is 1.

[0150] In another embodiment, the fluorine-containing compound in the surface treatment agent of the present disclosure is a compound represented by formula (1) in which α is 2.

[0151] In another embodiment, the fluorine-containing compound in the surface treatment agent of the present disclosure is a compound represented by formula (1) in which α is 1 and a compound represented by formula (1) in which α is 2.

[0152] In the surface treatment agent of the present disclosure, the content of the compound represented by formula (1) in which α is 2 relative to the total of the compound represented by formula (1) in which α is 1 and the compound represented by formula (1) in which α is 2 is preferably 0.1 mol % or more and 35 mol % or less. The lower limit of the content of the compound represented by formula (1) in which α is 2 relative to the total of the compound represented by formula (1) in which α is 1 and the compound represented by formula (1) in which α is 2 is preferably 0.1 mol %, more preferably 0.2 mol %, even more preferably 0.5 mol %, even more preferably 1 mol %, particularly preferably 2 mol %, and especially 5 mol %. The upper limit of the content of the compound represented by formula (1) in which α is 2 relative to the total of the compound represented by formula (1) in which α is 1 and the compound represented by formula (1) in which α is 2 is preferably 35 mol %, more preferably 30 mol %, even more preferably 20 mol %, and even more preferably 15 mol % or 10 mol %. The proportion of the compound represented by formula (1) where α is 2 relative to the total of the compound represented by formula (1) where α is 1 and the compound represented by formula (1) where α is 2 is preferably 0.1 mol % to 30 mol %, more preferably 0.1 mol % to 20 mol %, even more preferably 0.2 mol % to 10 mol %, still more preferably 0.5 mol % to 10 mol %, and particularly preferably 1 mol % to 10 mol %, for example, 2 mol % to 10 mol %, or 5 mol % to 10 mol %. By setting the proportion of the compound represented by formula (1) where α is 2 in this range, wear resistance can be further improved.

[0153] The content of the compound represented by formula (1) is preferably 0.1 to 50.0 mass%, more preferably 1.0 to 30.0 mass%, even more preferably 5.0 to 25.0 mass%, and particularly preferably 10.0 to 20.0 mass%, based on the total mass of the surface treatment agent. By setting the content of the fluorine-containing compound within the above range, higher water and oil repellency and friction durability can be obtained.

[0154] The surface treatment agent of the present disclosure may contain a solvent, a (non-reactive) fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter collectively referred to as a "fluorine-containing oil"), a (non-reactive) silicone compound that can be understood as a silicone oil (hereinafter referred to as a "silicone oil"), alcohols, a catalyst, a surfactant, a polymerization inhibitor, a sensitizer, etc.

[0155] Examples of the solvent include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, and ethyl 2-hydroxybutyrate. Esters such as ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, 2-heptanone; ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether ... Glycol ethers such as ethylene 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, and ethylene glycol monoalkyl ether; alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, and tert-amyl alcohol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; and diethylene glycol monoethyl ether acetate.Fluorine-containing solvents such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethyl sulfoxide, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), Zeorora H, HFE7100, HFE7200, HFE7300, CF3CH2OH, CF3CF2CH2OH, and (CF3)2CHOH are also included. Alternatively, mixed solvents of two or more of these solvents are also included.

[0156] The fluorine-containing oil is not particularly limited, but examples thereof include compounds represented by the following general formula (3) (perfluoro(poly)ether compounds). Rf 5 -(OC4F8) a’ -(OC3F6) b’ -(OC2F4) c’ -(OCF2) d’ -Rf 6 ···(3) In the formula, Rf 5 is an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms (preferably, C 1―16 Rf represents a perfluoroalkyl group 6 is an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms (preferably, C 1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom, and Rf 5 and Rf 6 More preferably, each independently represents C 1-3 It is a perfluoroalkyl group. a', b', c', and d' respectively represent the number of four types of repeating units of the perfluoro(poly)ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, and the sum of a', b', c', and d' is at least 1, preferably 1 to 300, and more preferably 20 to 300. The order of occurrence of each repeating unit enclosed in parentheses with the subscript a', b', c', or d' is arbitrary in the formula. Of these repeating units, -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and (OCF2CF(C2F5))-, but is preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-, but is preferably -(OCF2CF2CF2)-. -(OC2F4)- may be either -(OCF2CF2)- or (OCF(CF3))-, but is preferably -(OCF2CF2)-.

[0157] Examples of the perfluoro(poly)ether compound represented by the above general formula (3) include compounds represented by either of the following general formulas (3a) and (3b) (which may be one type or a mixture of two or more types): Rf 5 -(OCF2CF2CF2) b” -Rf 6 (3a) Rf 5 -(OCF2CF2CF2CF2) a” -(OCF2CF2CF2) b” -(OCF2CF2) c” -(OCF2) d” -Rf 6 (3b) In these formulas, Rf 5 and Rf 6is as defined above; in formula (3a), b" is an integer of 1 or more and 100 or less; in formula (3b), a" and b" are each independently an integer of 0 or more and 30 or less, and c" and d" are each independently an integer of 1 or more and 300 or less. The order of occurrence of each repeating unit enclosed in parentheses with the subscripts a", b", c", and d" is arbitrary in the formula.

[0158] From another perspective, the fluorine-containing oil is a compound represented by the general formula Rf 3 -F(where Rf 3 is C 5-16 It may be a compound represented by the formula: wherein R is a perfluoroalkyl group.) It may also be a chlorotrifluoroethylene oligomer.

[0159] The fluorine-containing oil may have an average molecular weight of 500 to 10000. The molecular weight of the fluorine-containing oil can be measured using GPC.

[0160] The fluorinated oil may be contained in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass, relative to the surface treatment agent of the present disclosure. In one embodiment, the surface treatment agent of the present disclosure is substantially free of fluorinated oil. "Substantially free of fluorinated oil" means that the surface treatment agent does not contain any fluorinated oil, or may contain a very small amount of fluorinated oil.

[0161] In one embodiment, the average molecular weight of the fluorinated oil may be larger than the average molecular weight of the fluorinated compound. By setting the average molecular weight in this manner, better abrasion resistance and surface slipperiness can be obtained, particularly when the surface treatment layer is formed by vacuum deposition.

[0162] In one embodiment, the average molecular weight of the fluorinated oil may be smaller than the average molecular weight of the fluorinated compound. By setting the average molecular weight in this range, it is possible to form a cured product having high abrasion resistance and high surface slipperiness while suppressing a decrease in the transparency of the surface treatment layer obtained from such a compound.

[0163] The fluorine-containing oil contributes to improving the surface slip properties of the layer formed by the surface treatment agent of the present disclosure.

[0164] As the silicone oil, for example, a linear or cyclic silicone oil having 2,000 or less siloxane bonds can be used. The linear silicone oil may be a so-called straight silicone oil or a modified silicone oil. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil.

[0165] In the surface treatment agent of the present disclosure, such silicone oil may be contained in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, relative to a total of 100 parts by mass of the fluorine-containing compounds of the present disclosure (the total of these when two or more types are used; the same applies hereinafter).

[0166] The silicone oil contributes to improving the surface slipperiness of the surface treatment layer.

[0167] Examples of the alcohols include alcohols having 1 to 6 carbon atoms which may be substituted with one or more fluorine atoms, such as methanol, ethanol, isopropanol, tert-butanol, CF3CH2OH, CF3CF2CH2OH, and (CF3)2CHOH. Adding these alcohols to the surface treatment agent improves the stability of the surface treatment agent and also improves the compatibility of the perfluorinated compound with the solvent.

[0168] The alcohol is preferably 2,2,3,3,3-pentafluoro-1-propanol or 2,2,2-trifluoroethanol.

[0169] Examples of the catalyst include acids (for example, acetic acid, trifluoroacetic acid, etc.), bases (for example, ammonia, triethylamine, diethylamine, etc.), and transition metals (for example, Ti, Ni, Sn, etc.).

[0170] The catalyst promotes the hydrolysis and dehydration condensation of the fluorine-containing compound of the present disclosure, and promotes the formation of the layer formed by the surface treatment agent of the present disclosure.

[0171] In addition to the above, other components include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane.

[0172] The surface treatment agent of the present disclosure can be impregnated into a porous substance, such as a porous ceramic material or a metal fiber, such as a flocculated steel wool, to form pellets, which can be used for vacuum deposition, for example.

[0173] In addition to the components described above, the surface treatment agent of the present disclosure may contain trace amounts of impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane condensates.

[0174] The articles of the present disclosure are described below.

[0175] The article of the present disclosure includes a substrate and a layer (surface treatment layer) formed on the surface of the substrate from the surface treatment agent of the present disclosure.

[0176] Substrates that can be used in the present disclosure may be made of any suitable material, such as glass, resin (which may be a natural or synthetic resin, for example, a common plastic material), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., building materials, etc., sanitary products, etc.

[0177] 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. Furthermore, if the article to be manufactured is an optical component, some layer (or film), such as a hard coat layer or an antireflection layer, may be formed on the surface (outermost layer) of the substrate. The antireflection layer may be either a single-layer antireflection layer or a multilayer antireflection layer. Examples of inorganic materials that can be used for the antireflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, Ta3O5, Nb2O5, HfO2, Si3N4, CeO2, MgO, YO3, SnO2, MgF2, and WO3. These inorganic materials may be used alone or in combination (e.g., as a mixture) of two or more of them. When a multilayer antireflection layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the product to be manufactured is an optical glass component for a touch panel, a transparent electrode, such as a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a portion of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, etc., depending on the specific specifications.

[0178] The shape of the substrate is not particularly limited and may be, for example, a plate, a film, or other form. The surface region of the substrate on which the surface treatment layer is to be formed may be at least a part of the substrate surface, and may be appropriately determined depending on the use and specific specifications of the product to be manufactured.

[0179] In one embodiment, at least the surface portion of such a substrate may be made of a material that originally contains hydroxyl groups. Examples of such materials include glass, metals (especially base metals), ceramics, semiconductors, and the like, on whose surfaces native oxide or thermal oxide films form. Alternatively, for materials such as resins, which do not have sufficient hydroxyl groups or do not originally contain hydroxyl groups, some pretreatment can be performed on the substrate to introduce or increase the number of hydroxyl groups on the surface. Examples of such pretreatments include plasma treatment (e.g., corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the substrate surface and can also be used to clean the substrate surface (remove foreign matter, etc.). Another example of such pretreatment is a method in which an interfacial adsorbent having carbon-carbon unsaturated bond groups is first formed in the form of a monomolecular film on the substrate surface by the Langmuir-Blodgett method (LB method) or chemical adsorption, followed by cleavage of the unsaturated bonds in an atmosphere containing oxygen, nitrogen, or the like.

[0180] In another embodiment, the substrate may have at least a surface portion made of a material containing another reactive group, such as a silicone compound having one or more Si—H groups, or an alkoxysilane.

[0181] In a preferred embodiment, the substrate is glass, such as sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, or quartz glass, with chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass being particularly preferred.

[0182] The article of the present disclosure can be produced by forming a layer of the surface treatment agent of the present disclosure on the surface of the substrate, and then post-treating this layer as necessary, thereby forming a layer from the surface treatment agent of the present disclosure.

[0183] The layer formation of the surface treatment agent of the present disclosure can be carried out by applying the surface treatment agent to the surface of a substrate so as to coat the surface. The coating method is not particularly limited. For example, a wet coating method or a dry coating method can be used.

[0184] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and similar methods.

[0185] Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum deposition) include resistance heating, electron beam, high frequency heating using microwaves, ion beam, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0186] Furthermore, coating by atmospheric pressure plasma method is also possible.

[0187] When using the wet coating method, the surface treatment agent of the present disclosure may be diluted with a solvent and then applied to the substrate surface. From the viewpoint of the stability of the composition 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 (e.g., CF 13CH2CH3 (e.g., Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeorora (registered trademark) H manufactured by Zeon Corporation); hydrofluoroethers (HFEs) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), Alkyl perfluoroalkyl ethers (the perfluoroalkyl group and alkyl group may be linear or branched) such as perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec™ 7200 manufactured by Sumitomo 3M Limited) and perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec™ 7300 manufactured by Sumitomo 3M Limited), or CF3CH2OCF2CHF2 (e.g., Asahiklin™ AE-3000 manufactured by Asahi Glass Co., Ltd.). These solvents can be used alone or as a mixture of two or more. Among them, hydrofluoroethers are preferred, with perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) being particularly preferred.

[0188] When the dry coating method is used, the surface treatment agent of the present disclosure may be subjected to the dry coating method as it is, or may be subjected to the dry coating method after being diluted with the above-mentioned solvent.

[0189] The layer formation of the surface treatment agent is preferably carried out so that the surface treatment agent of the present disclosure is present in the layer together with a catalyst for hydrolysis and dehydration condensation. Conveniently, in the case of a wet coating method, the surface treatment agent of the present disclosure may be diluted with a solvent, and then a catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure immediately before application to the substrate surface. In the case of a dry coating method, the surface treatment agent of the present disclosure to which the catalyst has been added may be directly subjected to vapor deposition (usually vacuum deposition), or a pellet-shaped material impregnated with the surface treatment agent of the present disclosure to which the catalyst has been added may be subjected to vapor deposition (usually vacuum deposition) on a porous metal such as iron or copper.

[0190] Any suitable acid or base can be used as the catalyst. Examples of acid catalysts that can be used include acetic acid, formic acid, and trifluoroacetic acid. Examples of base catalysts that can be used include ammonia and organic amines.

[0191] The surface treatment layer included in the article of the present disclosure has both high abrasion resistance and water repellency, oil repellency, antifouling properties (for example, preventing adhesion of stains such as fingerprints), waterproof properties (for example, preventing water penetration into electronic components), surface slipperiness (or lubricity, for example, ease of wiping off stains such as fingerprints and excellent tactile feel), chemical resistance, etc., depending on the composition of the surface treatment agent used, and can be suitably used as a functional thin film.

[0192] Therefore, the present disclosure also relates to an optical material having the above-described surface treatment layer as the outermost layer.

[0193] Preferred examples of the optical material include optical materials related to displays and the like, such as those exemplified below, as well as a wide variety of other optical materials: for example, displays such as cathode ray tubes (CRTs; for example, personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, vacuum fluorescent displays (VFDs), and field emission displays (FEDs), or protective plates for such displays, or displays whose surfaces have been treated with an anti-reflection film.

[0194] The article of the present disclosure may be, but is not particularly limited to, an optical member. Examples of optical members include lenses for eyeglasses and the like; front protective plates, anti-reflection plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; and the display surfaces of watches and clocks.

[0195] The article of the present disclosure may also be a medical device or medical material. The article having a layer obtained by the present disclosure may also be an automobile interior or exterior component. Examples of exterior components include windows, light covers, and exterior camera covers. Examples of interior components include instrument panel covers, navigation system touch panels, and decorative interior components.

[0196] The thickness of the layer is not particularly limited. In the case of optical members, the thickness of the layer is preferably in the range of 1 to 50 nm, preferably 1 to 30 nm, and more preferably 1 to 15 nm, from the viewpoints of optical performance, abrasion resistance, and antifouling properties.

[0197] The article of the present disclosure has been described in detail above. However, the article and the method for manufacturing the article of the present disclosure are not limited to the examples given above. [Example]

[0198] The article of the present disclosure will be described below in examples, but the present disclosure is not limited to the following examples. In these examples, the order of the repeating units constituting the fluoropolyether is arbitrary, and the chemical formula shown below indicates the average composition.

[0199] Synthesis Example 1 Synthesis of (FP-1) In a 300 mL four-neck flask equipped with a stirrer, dropping funnel, reflux condenser, and thermometer, and with the atmosphere purged with nitrogen, was placed a solution of HOCF2CF2-(OCF2) m(OCF2CF2) n 50 g of perfluoropolyether-containing alcohol (A) represented by O-CF2CF2OH (m = 20, n = 20) (including trace amounts of compounds containing a small amount of (CF2CF2CF2O) and / or (CF2CF2CF2CF2O) repeating units) and 4.5 g of trichlorotriazine were dissolved in 100 g of perfluorobenzene and then cooled to 0 ° C. Next, 3.7 g of diisopropylethylamine was added and the mixture was reacted at room temperature for 2 hours. Next, 10.4 g of 1-Boc-piperazine and 15.1 g of diisopropylethylamine were added, and the mixture was heated to 65 ° C. and stirred for 10 hours. After the reaction was completed, the organic layer was separated by a separation operation and evaporated under reduced pressure to obtain a reaction product of the perfluoropolyether-containing alcohol, trichlorotriazine, and 1-Boc-piperazine. The resulting reaction product was deprotected with 4.0 M hydrochloric acid in dioxane, neutralized, and then the organic layer was separated by a separation operation and evaporated under reduced pressure to obtain 56.6 g of a reaction product (FP-1) of perfluoropolyether-containing alcohol, trichlorotriazine, and piperazine.

[0200] Synthesis Example 2 Synthesis of (FD-1) The same procedure as in Synthesis Example 1 was repeated, except that 1-Boc-piperazine in Synthesis Example 1 was changed to diethanolamine. The mixture was stirred for 10 hours, and the organic layer was separated by a separation operation and evaporated under reduced pressure to obtain 52.4 g of a reaction product (FD-1) of perfluoropolyether-containing alcohol, trichlorotriazine, and diethanolamine.

[0201] Synthesis Example 3 Synthesis of (FP-1b) In a 300 mL four-neck flask equipped with a stirrer, dropping funnel, reflux condenser, and thermometer, 26.6 g of (A-1) and 0.04 g of dibutyltin dilaurate were dissolved in 80 g of 1,3-bis(trifluoromethyl)benzene. After thoroughly replacing the atmosphere in the system with nitrogen, 5.9 g of 1,1-(bisacryloyloxymethyl)ethyl isocyanate was added, the temperature was raised to 45°C, and the mixture was stirred for 8 hours. After the reaction was completed, the reaction solution was purified by reprecipitation to recover the fluoropolyether group-containing compound (FP-1b).

[0202] Comparative Example Synthesis Example 4 Synthesis of (FD-1b) A fluoropolyether group-containing compound (FD-1b) was recovered in the same manner as in Synthesis Example 3, except that (FP-1) in Synthesis Example 3 was changed to (FD-1).

[0203] evaluation Solubility Test The fluoropolyether group-containing compound obtained above was added to propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetone, ethyl acetate, and butyl acetate so that the solids concentration was 20 wt%. The mixture was stirred with a mixer rotor for 2 hours to dissolve the compound, and the solution state was visually inspected. The evaluation criteria were as follows. The results are shown in Table 1. ◎ Transparent and uniformly dissolved 〇 Almost transparently dissolved △ Slightly cloudy, slight sediment × Insoluble or turbid

[0204] [Table 1]

[0205] Example Beamset 575CB (manufactured by Arakawa Chemical Industries, Ltd.) (1.5 g) and methyl isobutyl ketone (1.5 g) were mixed, and the fluoropolyether group-containing compound FP-1b was added so that the amount was 0.5 mass % relative to the Beamset 575CB. The mixture was stirred in a rotary mixer under light shielding for 1 hour to obtain fluoropolyether-containing hard coat material 1 (Example 1).

[0206] Comparative Example A fluoropolyether-containing hard coat material 2 (Comparative Example 1) was obtained in the same manner as in the above Example, except that the fluoropolyether group-containing compound was changed to FD-1b.

[0207] (evaluation) <Evaluation of cured film properties> The hard coat materials 1 and 2 (1.0 ml) obtained above were placed on a PET film (Cosmoshine A4100, manufactured by Toyobo Co., Ltd.) cut to 1 / 4 the size of A4 paper, and a uniform coating film was formed using a bar coater. The obtained coating film was irradiated with 600 mJ / cm of light containing 365 nm UV light under a nitrogen atmosphere. 2 Each hard coat material was cured to obtain a cured film (surface treatment layer). The initial properties of these cured films were measured.

[0208] (exterior) The appearance of the cured film was visually inspected and evaluated according to the following criteria. The results are shown in Table 2. G: Transparent. NG: Whitening or foreign matter such as minute irregularities on the surface.

[0209] (Haze measurement) The haze of each cured film was measured. Specifically, a haze meter (Nippon Densyoku Co., Ltd., 7000SP) was used to measure three different points on the substrate according to the ASTM method, and the average value was calculated and used. The measurement results are shown in Table 2.

[0210] (static contact angle) The static contact angle was measured using a fully automatic contact angle meter, DropMaster 700 (Kyowa Interface Science Co., Ltd.), by dropping 2 μL of water from a microsyringe onto a horizontally placed substrate and taking a still image 1 second after the drop with a video microscope. The results are shown in Table 2.

[0211] [Table 2]

[0212] (Steel wool (SW) friction durability evaluation) Of the cured films, Example 1, which had a good appearance, was subjected to a steel wool friction durability evaluation. Specifically, the substrate on which the surface treatment layer was formed was placed horizontally, and steel wool (count #0000, dimensions 5 mm x 10 mm x 10 mm) was brought into contact with the surface treatment layer of the substrate. A load of 1,000 gf was applied thereto. Then, with the load applied, the steel wool was moved back and forth at a speed of 53.3 mm / s (friction speed 40 rpm). The static contact angle (degrees) of water was measured every 1,000 reciprocations, and the evaluation was stopped when the measured contact angle fell below 100 degrees. The number of reciprocations at which the contact angle finally exceeded 100 degrees is shown in Table 3.

[0213] (Eraser friction durability evaluation) Of the cured films, Example 1, which had a good appearance, was evaluated for friction durability by an eraser friction durability test. Specifically, the sample article on which the surface treatment layer was formed was placed horizontally, and an eraser (Minoan, hardness 81 (Durometer A type), circular with a planar dimension of 0.6 cm diameter) was brought into contact with the surface of the surface treatment layer, and a load of 1000 gf was applied thereon. Then, with the load applied, the eraser was moved back and forth at a speed of 48 mm / s (friction speed 40 rpm). The static contact angle (degrees) of water was measured every 1000 reciprocations. The evaluation was stopped when the measured contact angle became less than 100 degrees. The number of reciprocations at which the contact angle finally exceeded 100 degrees is shown in Table 3.

[0214] [Table 3] [Industrial Applicability]

[0215] The present disclosure can be suitably used to form a surface treatment layer on the surface of a wide variety of substrates.

Claims

1. The following formula (1): 【Chemical 1】 [In the formula: R １ is a divalent nitrogen-containing 5- to 8-membered ring, R Ａ are each independently —OCO—CR ３ =CH ２ is a group containing R ３ are each independently a hydrogen atom or a hydrocarbon group, R Ｂ is a monovalent or divalent group containing a fluoropolyether group, R Ｃ are each independently a hydrogen atom or a monovalent group, α is 1 or 2. A fluorine-containing compound represented by the formula:

2. R １ The fluorine-containing compound according to claim 1, wherein is 1,4-piperazinediyl.

3. R Ａ are each independently -X Ａ１ (-X Ａ２ (R Ａｃ ) Ａ２ ) Ａ１ and X Ａ１ represents a single bond or a divalent to pentavalent organic group, X Ａ２ are each independently a single bond or a divalent or trivalent organic group, A1 is X Ａ１ is the valence of -1, A2 is X Ａ２ is the valence of -1, R Ａｃ are each independently —OCO—CR ３ =CH ２ and R ３ are each independently a hydrogen atom or a hydrocarbon group; The fluorine-containing compound according to claim 1.

4. X Ａ１ The fluorine-containing compound according to claim 3 , wherein is a single bond.

5. X Ａ１ The divalent to pentavalent organic group in Ａ１１ -R Ａ１２ - or -R Ａ１３ (-R Ａ１２ ) ２ and R Ａ１１ is C １－２０ Alkylene group, -(CH ２ ) ｚ１ -O-(CH ２ ) ｚ２ - (wherein z1 is an integer from 0 to 10, and z2 is an integer from 0 to 10), or -(CH ２ ) ｚ３ -phenylene-(CH ２ ) ｚ４ - (wherein z3 is an integer from 0 to 10, and z4 is an integer from 0 to 10), R Ａ１２ is —O—, —CO—, or —NR １１ - and R １１ is a hydrogen atom or a hydrocarbon group, R Ａ１３ is a trivalent C １－１０ Hydrocarbon group or trivalent C １－１０ a group containing one or more O in the main chain of a hydrocarbon group; The fluorine-containing compound according to claim 3.

6. X Ａ２ is -CO-NH-C(R １３ ) (R １４ ) ２ and R １３ is a hydrogen atom or C １－６ is an alkyl group, R １４ are each independently C １－６ is an alkylene group, The fluorine-containing compound according to claim 3.

7. R Ｂ is -X Ｂ１ -R Ｆ１ , or -X Ｂ１ -R Ｆ２ -X Ｂ１ - and R Ｆ１ is a monovalent fluoropolyether group, R Ｆ２ is a divalent fluoropolyether group, X Ｂ１ are each independently a single bond or a divalent organic group; The fluorine-containing compound according to claim 1.

8. R Ｆ１ is Rf １ -R Ｆ -O ｑ - and R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ - and Rf １ is a C optionally substituted by one or more fluorine atoms; １－１６ is an alkyl group, Rf ２ is a C optionally substituted by one or more fluorine atoms; １－６ is an alkylene group, R Ｆ are each independently a divalent fluoropolyether group, p is 0 or 1; Each q is independently 0 or 1; The fluorine-containing compound according to claim 7.

9. R Ｆ are each independently a group having the formula: -(OC ６ F １２ ) ａ -(OC ５ F １０ ) ｂ -(OC ４ F ８ ) ｃ -(OC ３ R Ｆａ ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - [In the formula: R Ｆａ are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, a, b, c, d, e, and f each independently represent an integer of 0 to 200, the sum of a, b, c, d, e, and f is 1 or more, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] The fluorine-containing compound according to claim 8 , wherein the fluorine-containing compound is a group represented by the formula:

10. R Ｆａ The fluorine-containing compound according to claim 9 , wherein is a fluorine atom.

11. R Ｆ are each independently represented by the following formula (f1), (f2), (f3), (f4), (f5) or (f6): -(OC ３ F ６ ) ｄ -(OC ２ F ４ ) ｅ - (f1) [wherein d is an integer of 1 to 200, and e is 0 or 1.] -(OC ４ F ８ ) ｃ -(OC ３ F ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f2) [In the formula, c and d each independently represent an integer of 0 to 30; e and f are each independently an integer from 1 to 200; The sum of c, d, e, and f is an integer from 10 to 200; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula. -(R ６ -R ７ ) ｇ -R ９ - (f3) [In the formula, R ６ is OCF ２ or O.C. ２ F ４ and R ７ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups selected from these groups; R ９ is a single bond or OCF ２ , O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups selected from these groups; g is an integer from 2 to 100. -(R ６ -R ７ ) ｇ -R ｒ -(R ７’ -R ６’ ) ｇ’ - (f4) [In the formula, R ６ is OCF ２ or O.C. ２ F ４ and R ７ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups, R ６’ is OCF ２ or O.C. ２ F ４ and R ７’ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100, g' is an integer from 2 to 100, R ｒ teeth, 【Chemistry 2】 (In the formula, * indicates the bonding position.) is. ]; -(OC ６ F １２ ) ａ -(OC ５ F １０ ) ｂ -(OC ４ F ８ ) ｃ -(OC ３ F ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f5) [In the formula, e is an integer of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] -(OC ６ F １２ ) ａ -(OC ５ F １０ ) ｂ -(OC ４ F ８ ) ｃ -(OC ３ F ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f6) [In the formula, f is an integer of 1 or more and 200 or less, a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] The fluorine-containing compound according to claim 8 , wherein the fluorine-containing compound is a group represented by the formula:

12. Rf １ are each independently C １－１６ is a perfluoroalkyl group, Rf ２ are each independently C １－６ is a perfluoroalkylene group, The fluorine-containing compound according to claim 8.

13. X Ｂ１ are each independently represented by the following formula: -(CX １２１ X １２２ ) ｂ１ -(X Ｂ１ａ ) ｂ２ -(CX １２３ X １２４ ) ｂ３ - [In the formula, X １２１ ~X １２４ are each independently H, C １－６ an alkyl group or a halogen; X Ｂ１ａ is —C(═O)NH—, —NHC(═O)—, —O—, —C(═O)O—, —OC(═O)—, —OC(═O)O—, or —NHC(═O)NH—, b1 is an integer from 0 to 10, b2 is 0 or 1, b3 is an integer from 0 to 10, and the sum of b1, b2, and b3 is at least 1. The fluorine-containing compound according to claim 7, wherein the fluorine-containing compound is a group represented by the formula:

14. X Ｂ１ are each independently —O—(CH ２ ) ｍ１１ - and m11 is an integer from 1 to 6. The fluorine-containing compound according to claim 7.

15. The fluorine-containing compound according to claim 1 , wherein α is 1.

16. R Ｃ is -R １ -R Ａ The fluorine-containing compound according to claim 1, wherein

17. A surface treatment agent comprising one or more compounds according to any one of claims 1 to 16.

18. The surface treatment agent according to claim 17, which is used as an antifouling coating agent or a waterproof coating agent.

19. An article comprising a substrate and a layer formed on the surface of the substrate using the surface treatment agent according to claim 17.

20. 20. The article of claim 19, wherein the article is an optical element.

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