Fluoropolyether group-containing silane compound

Abstract

To provide a fluoropolyether group-containing silane compound that can contribute to forming a surface-treated layer having improved physical properties.SOLUTION: The present invention provides a fluoropolyether group-containing silane compound represented by formula (A1) or (A2) (where, the respective symbols are as described in the specifications).SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a fluoropolyether group-containing silane compound.

Background Art

[0002] It is known that certain fluorine-containing silane compounds can provide excellent water repellency, oil repellency, antifouling properties, etc. when used for surface treatment of a substrate. A layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter also referred to as "surface treatment layer") is applied as a so-called functional thin film to various substrates such as glass, plastic, fiber, building materials, etc.

[0003] As such a fluorine-containing compound, a fluoropolyether group-containing silane compound having a fluoropolyether group in the molecular main chain and a hydrolyzable group bonded to the Si atom at the molecular end or end portion is known (Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The above surface treatment layer is required to have further better physical properties. The present disclosure provides a fluoropolyether group-containing silane compound that can contribute to the formation of a surface treatment layer having better physical properties.

Means for Solving the Problems

[0006] The present disclosure provides the following [1] to

[19] . [1] The following formula (A1) or (A2):

Chemical formula

Chemical formula

[10] n55 is 1, a fluoropolyether group-containing silane compound according to any one of [1] to [9].

[11] n54 and n55 are 0, a fluoropolyether group-containing silane compound according to any one of [1] to [9].

[12] A surface treatment agent containing at least one selected from the group consisting of a fluoropolyether group-containing silane compound according to any one of [1] to

[11] , and a condensate in which at least a part of the fluoropolyether group-containing silane compound is condensed.

[13] A surface treatment agent containing the fluoropolyether group-containing silane compound according to any one of [1] to

[11] .

[14] An article comprising a substrate and a layer formed on the surface of the substrate from the fluoropolyether group-containing silane compound according to any one of [1] to

[11] or the surface treatment agent according to

[12] or

[13] .

[15] Formula (a11) or formula (a12):

Chemical formula

Chemical formula

Chemical formula

[16] Formula (a31) or formula (a32):

Chemical formula

Chemical formula

Chemical formula

[17] Formula (a23), or formula (a24):

Chemical formula

Chemical formula

[18] Formula (a23) or formula (a24):

Chemical formula

[19] Formula (a27) or formula (a28): [ka] A fluoropolyether group-containing compound represented by the formula: [In formula: R F1 is Rf 1 -R F -O q - represented by; R F2 is -Rf 2 p -R F -O q - represented by; 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 may independently in each occurrence represent the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - is a group represented by the formula: 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; R Fa is independently in each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom; p is 0 or 1; q is independently 0 or 1; -X 6 -, independently in each occurrence, -X61 -CR 61 =CR 62 -X 62 -,or -X 63 - Represented by; X 61 are each independently -(CR 60 2) n611 -((CH2) n614 -Y 61 -(CH2) n613 ) n612 - Represented by; R 60 represents, independently in each occurrence, a hydrogen atom, a halogen atom, or a monovalent organic group; Y 61 independently in each occurrence, O, CONR 15 , N.R. 15 , S, or an arylene group; n613 are each independently 0 or 1; n614 are each independently 0 or 1; n611 is an integer from 0 to 10; n612 is an integer from 0 to 10; The order of occurrence of each repeating unit enclosed in parentheses with n611 or n612 is arbitrary in the formula; X 62 are each independently -(CR 60 2) n611’ -((CH2) n614 -Y 61 -(CH2) n613 ) n612’ - represented by; n611' is an integer from 0 to 10; n612' is an integer from 0 to 10; The order of occurrence of each repeating unit enclosed in parentheses with n611' or n612' is arbitrary in the formula; R 15 each occurrence independently represents a hydrogen atom, a group having an aromatic ring, C 1-6 Alkyl group, -OC1-6 is an alkyl group or a C 3-10 cycloalkyl group; R 61 and R 62 are each independently a hydrogen atom or a monovalent organic group; X 63 is -(CR 60 2) n621 -((CH2) n614 -Y 61 -(CH2) n613 ) n622 - represented by; n621 is an integer from 0 to 10; n622 is an integer from 0 to 10; The order of existence of each repeating unit enclosed in parentheses with n621 or n622 is arbitrary in the formula, and the sum of n621 and n622 is 1 or more; R 65 are each independently a hydrogen atom or a monovalent organic group; Z 23 each independently represents a single bond or a divalent organic group.]

Advantages of the Invention

[0007] According to the present disclosure, a fluoropolyether group-containing silane compound that can contribute to the formation of a surface treatment layer having better physical properties can be provided.

Modes for Carrying Out the Invention

[0008] As used herein, the term "monovalent organic group" means a monovalent group containing carbon. The monovalent organic group is not particularly limited, and may be a hydrocarbon group or a derivative thereof. The derivative of a hydrocarbon group means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the terminal or in the molecular chain of the hydrocarbon group. As used herein, the "divalent organic group" is not particularly limited, and examples thereof include divalent groups obtained by further removing one hydrogen atom from a hydrocarbon group.

[0009] As used herein, the "hydrocarbon group" means a group containing carbon and hydrogen and obtained by removing one hydrogen atom from a molecule. Such hydrocarbon groups are not particularly limited, and examples thereof include hydrocarbon groups having 1 to 20 carbon atoms, which may be substituted with one or more substituents, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The above "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Further, the hydrocarbon group may contain one or more ring structures. Incidentally, such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at its terminal or in the molecular chain.

[0010] As used herein, the substituents of the "hydrocarbon group" are not particularly limited, and examples thereof include halogen atoms; C alkyl groups, C alkenyl groups, C alkynyl groups, C cycloalkyl groups, unsaturated cycloalkyl groups, 5- to 10-membered heterocyclyl groups, 5- to 10-membered unsaturated heterocyclyl groups, C aryl groups, and 5- to 10-membered heteroaryl groups, which may be substituted with one or more halogen atoms. 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 aryl group and one or more groups selected from 5- to 10-membered heteroaryl groups.

[0011] In this specification, unless otherwise specified, the alkyl group and the phenyl group may be unsubstituted or substituted. The substituents of such groups are not particularly limited, and examples thereof include halogen atoms, C alkyl groups, C alkenyl groups, and C alkynyl groups, and one or more groups selected therefrom. 1-6 alkyl group, C 2-6 alkenyl group and C 2-6 alkynyl group.

[0012] As used herein, the term "hydrolyzable group" refers to a group that can undergo a hydrolysis reaction, i.e., a group that can be removed from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include -OR h , -OCOR h , -ON=CR h 2, -NR h 2, -NHR h , —NCO, halogen (wherein R h is a substituted or unsubstituted C 1-4 alkyl group), and preferably -OR h1 (i.e., an alkoxy group). h1 Examples of the hydrolyzable group include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among them, alkyl groups, particularly unsubstituted alkyl groups, are preferred, with methyl or ethyl groups being more preferred. In one embodiment, the hydrolyzable group is a methoxy group. In another embodiment, the hydrolyzable group is an ethoxy group.

[0013] (Fluoropolyether group-containing silane compound) The fluoropolyether group-containing silane compound of the present disclosure is a compound represented by the following formula (A1) or (A2). [ka]

[0014] In formula (A1), R F1 is Rf 1 -R F -O q - is expressed as

[0015] In formula (A2), R F2 is -Rf 2 p -R F -O q - is expressed as

[0016] Rf 1 C optionally substituted with one or more fluorine atoms 1-16 It is an alkyl group.

[0017] 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 1-3 It is an alkyl group.

[0018] Above Rf 1 is preferably C substituted by one or more fluorine atoms 1-16 alkyl group, more preferably CF2H-C 1-15 A perfluoroalkylene group, more preferably C 1-16 It is a perfluoroalkyl group.

[0019] Above C 1-16 The perfluoroalkyl group may be a straight or branched chain, and is preferably a straight or branched C 1-6 Perfluoroalkyl groups, especially C 1-3 A perfluoroalkyl group, more preferably a linear C 1-6 Perfluoroalkyl groups, especially C 1-3 A perfluoroalkyl group, specifically -CF3, -CF2CF3, or -CF2CF2CF3.

[0020] Rf 2 C optionally substituted with one or more fluorine atoms 1-6 It is an alkylene group.

[0021] C optionally substituted with one or more fluorine atoms 1-6 "C" in the alkylene group1-6 The "alkylene group" may be linear or branched, preferably a linear or branched C 1-3 alkylene group, more preferably a linear C 1-3 alkylene group.

[0022] The above Rf 2 is preferably a C 1-6 alkylene group substituted by one or more fluorine atoms, more preferably a C 1-6 perfluoroalkylene group, even more preferably a C 1-3 perfluoroalkylene group.

[0023] The above C 1-6 perfluoroalkylene group may be linear or branched, preferably a linear or branched C 1-3 perfluoroalkylene group, more preferably a linear C 1-3 perfluoroalkylene group, specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0024] In the above formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0025] In the above formula, q is independently 0 or 1 at each occurrence. In one embodiment, q is 0. In another embodiment, q is 1.

[0026] In the above formulas (A1) and (A2), R F is, at each occurrence, independently a fluoropolyether group represented by the following formula. Note that the structure described as R F is bonded to the structure represented by Rf 1 on the left side in formula (A1), and is bonded to the structure represented by Rf 2 p on the left side in formula (A2). -(OC6F 12 ) a -(OC5F10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [wherein: R Fa is, in each occurrence, independently a hydrogen atom, a fluorine atom or a chlorine atom, a, b, c, d, e and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula.]

[0027] R Fa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom.

[0028] a, b, c, d, e and f may preferably each independently be an integer from 0 to 100.

[0029] 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, still more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0030] These repeating units may be linear or branched, but are preferably linear. For example, -(OC6F 12 )- may be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))- etc., but is preferably -(OCF2CF2CF2CF2CF2CF2)-. -(OC5F10 )- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc., but is preferably -(OCF2CF2CF2CF2CF2CF2)-. -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)- and -(OCF2CF(C2F5))-, but is preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- (i.e., in the above formula, R Fa is a fluorine atom) may be any of -(OCFCFCF)-, -(OCF(CF)CF)-, and -(OCFCF(CF))-, but is preferably -(OCFCFCF)-. Also, -(OCF)- may be any of -(OCFCF)- and -(OCF(CF))-, but is preferably -(OCFCF)-.

[0031] In one embodiment, R F is each independently in each occurrence a formula (f1), (f2), (f3), (f4) or (f5): -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer of 1 to 200, and e is 0 or 1, preferably 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; and g is an integer from 2 to 100. -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f4) [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, the sum of a, b, c, d, e, and f is at least 1, 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 - (f5) [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, the sum of a, b, c, d, e, and f is at least 1, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] is a group represented by

[0032] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, still more preferably 15 to 50, for example 25 to 35. (OC3F6) in the above formula (f1) is preferably a group represented by (OCF2CF2CF2) or (OCF(CF3)CF2), and more preferably a group represented by (OCF2CF2CF2). (OC2F4) in the above formula (f1) is preferably a group represented by (OCF2CF2) or (OCF(CF3)), and more preferably a group represented by (OCF2CF2).

[0033] In the above formula (f2), e and f are each independently preferably an integer of 5 or more and 200 or less, more preferably 10 to 200. Also, 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 aspect, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f -represented group. In another aspect, formula (f2) may be a group represented by -(OC2F4) e -(OCF2) f -represented group.

[0034] In the above formula (f3), R 6 is preferably OC2F4. In the above (f3), R 7is 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.

[0035] In the above formula (f4), e 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.

[0036] In the above formula (f5), f 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.

[0037] In one embodiment, the R F is a group represented by the above formula (f1).

[0038] In one embodiment, the R F is a group represented by the above formula (f2).

[0039] In one embodiment, the R F is a group represented by the above formula (f3).

[0040] In one embodiment, the R F is a group represented by the above formula (f4).

[0041] In one embodiment, the R F is a group represented by the above formula (f5).

[0042] In a preferred embodiment, R F is the formula (f2): -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - 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, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and the order of occurrence of each repeating unit enclosed in parentheses with the subscript e or f is arbitrary in the formula. F More specifically, -(OC2F4) e -(OCF2) f - may be a group represented by the formula:

[0043] Above R FIn this case, the ratio of e to f (hereinafter referred to as "e / f ratio") is from 0.1 to 10, preferably from 0.2 to 5, more preferably from 0.2 to 2, still more preferably from 0.2 to 1.5, and even more preferably from 0.2 to 0.85. By setting the e / f ratio to 10 or less, R F The slipperiness, friction durability, and chemical resistance (for example, durability against artificial sweat) of the cured layer (for example, the surface treatment layer) obtained from the compound containing F 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 above compound can be further enhanced. The larger the e / f ratio, the more improved the stability of the above compound. In this case, the value of f is 1 or more.

[0044] In one aspect, the e / f ratio is preferably from 0.2 to 0.95, more preferably from 0.2 to 0.9.

[0045] In one aspect, the e / f ratio is preferably 0.20 or more and less than 1.0, more preferably from 0.20 to 0.95, still more preferably from 0.20 to 0.90, even more preferably from 0.40 to 0.80, and particularly preferably from 0.50 to 0.70.

[0046] In one aspect, the e / f ratio is preferably from 0.20 to 0.80, more preferably from 0.30 to 0.70. In another aspect, the e / f ratio is from 0.50 to 0.80.

[0047] In one aspect, from the viewpoint of heat resistance, the e / f ratio is preferably 1.0 or more, more preferably from 1.0 to 2.0.

[0048] In one aspect, the e / f ratio is from 0.2 to 1.5, preferably from 0.5 to 1.1.

[0049] The above R FIn this case, the e / f ratio may be less than 1.0, may be 0.95 or less, may be 0.90 or less, may be less than 0.90, for example, 0.8 or less, or may be 0.70 or less. The e / f ratio is preferably 0.20 or more, more preferably 0.30 or more, still more preferably 0.40 or more, and particularly preferably 0.50 or more. The e / f ratio can be, for example, 0.20 or more and less than 1.0, for example, 0.20 or more and 0.95 or less, 0.20 or more and less than 0.90, specifically 0.40 or more and 0.80 or less, and more specifically 0.50 or more and 0.70 or less. If the e / f ratio becomes too low, the hydrolyzability of the cured layer (or cured film; the same applies hereinafter) formed using the fluoropolyether group-containing silane compound of the present disclosure may increase, and the durability of the cured layer may decrease. If the e / f ratio becomes too high, the coefficient of kinetic friction of the cured layer formed using the fluoropolyether group-containing silane compound of the present disclosure may increase, and a cured layer having sufficient friction durability may not be obtained.

[0050] In a preferred embodiment, R F is -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) is a group represented by (wherein c and d are each independently an integer of 0 or more and 30 or less, and e and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and the order of existence of each repeating unit enclosed in parentheses with subscript e or f is arbitrary in the formula), and the e / f ratio is 0.20 or more and less than 1.0, more preferably 0.20 to 0.95, more preferably 0.20 to 0.90, still more preferably 0.40 to 0.80, and particularly preferably 0.50 to 0.70. R F is more specifically a group represented by -(OC2F4) e -(OCF2) f -. R as described above FBy using a compound having the following, the chemical durability (chemical resistance), frictional durability, water repellency, oil repellency, antifouling property (e.g., preventing the adhesion of dirt such as fingerprints), waterproof property (preventing the intrusion of water into electronic components, etc.), or surface slipperiness (or lubricity, e.g., the wipe-off property of dirt such as fingerprints and the excellent touch feeling against fingers) of the cured layer formed using the compound becomes good. This is because, as described above, for the compound having R F It is considered that by using a compound having the following, the coefficient of kinetic friction of the surface of the cured layer formed from the compound becomes small.

[0051] In one embodiment, R F is -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) a group represented by (wherein c and d are each independently an integer of 0 or more and 30 or less, and e and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and the order of existence of each repeating unit enclosed in parentheses with subscript e or f is arbitrary in the formula), The e / f ratio is 0.20 to 0.80, more preferably 0.30 to 0.70.

[0052] In one embodiment, e may be an integer of 10 or more and 100 or less, and f may be an integer of 11 or more and 100 or less, or e may be an integer of 15 or more and 70 or less, and f may be an integer of 21 or more and 95 or less.

[0053] In one embodiment, the sum of e and f is preferably 20 or more, more preferably 30 or more, particularly preferably 40 or more.

[0054] In another embodiment, the sum of e and f is preferably 100 or more, more preferably 120 or more, still more preferably 130 or more, particularly preferably 140 or more.

[0055] In one embodiment, the sum of e and f is preferably 200 or less, more preferably 180 or less, even more preferably 160 or less, and particularly preferably 150 or less.

[0056] R F1 and R F2 The number average molecular weight of the R moiety is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,500 to 30,000, and even more preferably 4,000 to 30,000. F1 and R F2 The number average molecular weight of the moiety may be, for example, 2,500 to 20,000, 2,500 to 15,000, 3,000 to 15,000, or 2,000 to 10,000. F1 and R F2 The number average molecular weight of 19 The value is measured by F-NMR.

[0057] In another embodiment, R F1 and R F2 The number average molecular weight of the moiety may be from 500 to 30,000, preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, even more preferably from 2,000 to 10,000, for example from 3,000 to 6,000.

[0058] In another embodiment, R F1 and R F2 The number average molecular weight of the R moiety may be 6,000 to 30,000, preferably 6,000 to 20,000, more preferably 7,000 to 20,000, even more preferably 8,000 to 15,000, particularly preferably 9,000 to 15,000, and more preferably 10,000 to 15,000. F1 and R F2 The number average molecular weight of the moiety may be, for example, in the range of 6,000 to 15,000.

[0059] In one embodiment, in the fluoropolyether group-containing silane compound of the present disclosure, R F1and R F2 The number average molecular weight of the part is in the range of 6,000 to 20,000, and the e / f ratio is in the range of 0.50 to 0.80; Preferably, R F1 and R F2 The number average molecular weight of the part is in the range of 6,000 to 15,000, and the e / f ratio is in the range of 0.50 to 0.70; More preferably, R F1 and R F2 The number average molecular weight of the part is in the range of 10,000 to 15,000, and the e / f ratio is in the range of 0.50 to 0.70. In this embodiment, preferably, R F is a group represented by -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -. Here, for example, c and d are each independently an integer of 0 or more and 30 or less, e is an integer in the range of 20 to 70, and f is an integer in the range of 45 to 120. Such a fluoropolyether group-containing silane compound can contribute to the formation of a cured layer (for example, a surface treatment layer) exhibiting extremely high lubricity and slipperiness due to a low kinetic friction coefficient.

[0060] In the present disclosure, R F1 or R F2 The group represented by and CR Si 2(OR 11 ) are bonded by a group represented by -X 1 -. Here, the group represented by R F1 or R F2 is a group containing a fluoropolyether group that mainly provides water repellency and surface slipperiness, etc., and the group represented by CR Si 2(OR 11 ) contains a silane part that provides the bonding ability to the substrate. X 1 is, in each occurrence, independently, the following formula (X): -(CR 50 2) n51 -(CR 51 =CR 52 ) n52 -((CH2)n55 -Y 51 -(CH2) n54 ) n53 - (X) It is expressed as: 1 By having such a structure, the cured layer formed using the fluoropolyether group-containing silane compound represented by formula (A1) and / or the fluoropolyether group-containing silane compound represented by formula (A2) can have good flexibility, abrasion resistance, wettability on a substrate, and adhesion to a substrate. In this specification, X 1 The left side of the structure is R F1 or R F2 The group represented by and the right side is CR Si 2(OR 11 ) and bond to a group represented by the formula:

[0061] n51 is an integer of 0 to 10, and preferably an integer of 0 to 5. n52 is an integer of 0 to 10, and preferably an integer of 0 to 5. n53 is an integer of 0 to 10, and preferably an integer of 0 to 5. However, the order of the repeating units enclosed in parentheses with n51, n52 or n53 is arbitrary in the formula, and the sum of n51, n52 and n53 is 1 or more.

[0062] In one embodiment, n51 is an integer of 1 to 10, for example, an integer of 1 to 6.

[0063] In one embodiment, n51 is an integer of 1 to 5. In one embodiment, n51 is 2.

[0064] In one embodiment, n51 is an integer of 3 to 5, for example 4 or 5.

[0065] In one embodiment, n51 is an integer of 1 to 10, preferably an integer of 1 to 5; n52 and n53 are 0.

[0066] In one aspect, n51 is an integer from 3 to 5, for example 4 or 5; n52 and n53 are 0.

[0067] n54 is, independently of each other, 0 or 1.

[0068] n55 is, independently of each other, 0 or 1.

[0069] In one aspect, n51 is an integer from 1 to 10, preferably an integer from 1 to 5; n52 is 0; n53 is 1. In this aspect, for example, n54 is 1.

[0070] In one aspect, n51 is 0; n52 is 0; n53 is 1. In this aspect, for example, n54 is 1.

[0071] In one aspect, n51 is an integer from 1 to 10, preferably an integer from 1 to 5; n52 is 0; n53 is 1. In this aspect, for example, n54 is 0.

[0072] In one aspect, n54 is 0 or 1.

[0073] In one aspect, n55 is 0 or 1.

[0074] In one aspect, n55 is 1.

[0075] In another aspect, n54 and n55 are 0.

[0076] R 51 is, independently of each other, a hydrogen atom, or a monovalent organic group, preferably a hydrogen atom, or a C 1-3 alkyl group. In one aspect, R 51 is a hydrogen atom. In one aspect, R 51 is a methyl group.

[0077] R 52is independently in each occurrence a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or 1-3 It is an alkyl group. In one embodiment, R 52 is a hydrogen atom. In one embodiment, R 52 is a methyl group.

[0078] In one embodiment, R 51 and R 52 is a hydrogen atom.

[0079] Y 51 independently in each occurrence, O, CONR 15 , N.R. 15 , S, or an arylene group, preferably O, CONR 15 , or NR 15 and more preferably O. R 15 each occurrence independently represents a hydrogen atom, a group having an aromatic ring, C 1-6 Alkyl group, -OC 1-6 Alkyl group or C 3-10 It is a cycloalkyl group, preferably a hydrogen atom. An example of a group having an aromatic ring is a phenyl group. Examples of the arylene group include C 6-10 Examples of the phenylene group include an arylene group, and specifically, a phenylene group having a substituent. The substituent may be a halogen atom, an alkyl group (e.g., C 1-4 alkyl group), a monovalent group derived from a heterocycle (for example, a monovalent group derived from piperidine, piperazine, morpholine, dioxane, dithiane, pyrrolidine, oxazolidine, isoxazolidine, thiazolidine, isothiazolidine, imidazolidine, or pyrazolidine), or a phenoxy group. In addition, Y 51 When Y has a ring structure, 51 and X 1 or Y 51 and R F1 , R F2or the bonding position with CRSi2(OR 11 ) is not particularly limited.

[0080] In one embodiment, Y 51 is O. In one embodiment, Y 51 is a phenylene group.

[0081] In one embodiment, Y 51 is CONR 15 .

[0082] R 50 is, in each occurrence, independently a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group.

[0083] In one embodiment, R 50 is a hydrogen atom. In one embodiment, R 50 is a halogen atom. In one embodiment, R 50 is a monovalent organic group.

[0084] R 50 is preferably, in each occurrence, independently a hydrogen atom, a halogen atom (e.g., F, Cl, Br, I), a hydroxyl group, -O-(R 14 -O) n4 -R 14’ , or a C 1-4 alkyl group. In the formula, R 14 is, in each occurrence, independently a C 1-4 alkylene group, n4 is, in each occurrence, independently an integer from 0 to 100, preferably an integer from 1 to 50, more preferably an integer from 1 to 40, and even more preferably an integer from 1 to 10, R 14’ is, in each occurrence, independently a C 1-4 alkyl group. Here, the C 1-4 alkyl group may have a substituent.

[0085] In one embodiment, R 50is, independently of each other, a hydrogen atom, a halogen atom, or a C 1-4 alkyl group.

[0086] In one embodiment, R 50 is, independently of each other, a hydrogen atom, a halogen atom (e.g., F, Cl, Br, I), a hydroxyl group, -O-(R 14 -O) n4 -R 14’ or a C 1-4 alkyl group (e.g., a methyl group), and for example, independently of each other, a hydrogen atom, a hydroxyl group, -O-(R 14 -O) n4 -R 14’ or a C 1-4 alkyl group. R 14 is, independently of each other, a C 1-4 alkylene group, n4 is, independently of each other, an integer from 0 to 100, preferably an integer from 1 to 50, more preferably an integer from 1 to 40, even more preferably an integer from 1 to 10, R 14’ is, independently of each other, a C 1-4 alkyl group. Here, the C 1-4 alkyl group may have a substituent.

[0087] In one embodiment, X 1 is, in each occurrence, independently represented by the following formula (X1) or (X2). -X 51 -CR 51 =CR 52 -X 52 - ···(X1) -X 53 - ···(X2)

[0088] In formula (X1), X 51 is -(CR 50 2) n511 -((CH2) n55 -Y 51 -(CH2) n54 ) n512- It is expressed as: R 50 , Y 51 , n54 and n55 have the same meanings as above. n511 is an integer of 0 to 10, and preferably an integer of 0 to 5. n512 is an integer of 0 to 10, and preferably an integer of 0 to 5. The repeating units enclosed in parentheses with n511 or n512 may be present in any order in the formula. In one embodiment, the sum of n511 and n512 is 1 or greater. In one embodiment, n511 is an integer from 1 to 10, and n512 is 0. In other words, X 51 Ha-(CR 50 2) n511 - is expressed as

[0089] In one embodiment, n511 is an integer of 1 to 10, and preferably an integer of 1 to 5.

[0090] In one embodiment, n511 is an integer of 3 to 5, for example 4 or 5.

[0091] In one embodiment, n511 is an integer of 1 to 10, preferably an integer of 1 to 5;

[0092] X 51 is preferably -(CR 50 2) n514 -((CH2) n55 -Y 51 -(CH2) n54 )-(CR 50 2) n515 n514 is an integer of 0 to 10, and n515 is an integer of 0 to 10, more preferably, n514 is an integer of 0 to 5, and n515 is an integer of 0 to 5. The sum of n514 and n515 corresponds to n511. R 50 , n54, n55, and Y 51 has the same meaning as above.

[0093] X52 are each independently -(CR 50 2) n511’ -((CH2) n55 -Y 51 -(CH2) n54 ) n512’ - represented by. R in X 52 and Y 50 are synonymous with R in X 51 and Y 51 respectively. 50 and Y 51 are each synonymous. n511’ is an integer from 0 to 10, preferably an integer from 0 to 5. n512’ is an integer from 0 to 10, preferably an integer from 0 to 5. However, the order of existence of each repeating unit enclosed in parentheses with n511’ or n512’ is arbitrary in the formula. In one embodiment, the sum of n511’ and n512’ is 1 or more. In one embodiment, n511’ is an integer from 1 to 10 and n512’ is 0. In other words, X 52 is represented by -(CR 50 2) n511’ -.

[0094] In one embodiment, n511’ is an integer from 1 to 10, preferably an integer from 1 to 5.

[0095] In one embodiment, n511’ is an integer from 3 to 5, such as 4 or 5.

[0096] In one embodiment, n511’ is an integer from 1 to 10, preferably an integer from 1 to 5; n512’ is 0.

[0097] In one embodiment, the sum of n511, n512, n511’ and n512’ is 1 or more.

[0098] In one embodiment, X 52 is -(CR 50 2)n514’ -((CH2) n55 -Y 51 -(CH2) n54 )-(CR 50 2) n515’ - is represented by. n514’ is an integer from 0 to 10, n515’ is an integer from 0 to 10, more preferably, n514’ is an integer from 0 to 5, and n515’ is an integer from 0 to 5.

[0099] In one embodiment, n514’ is an integer from 0 to 10, n515’ is an integer from 1 to 10. For example, n514’ is an integer from 0 to 5, and n515’ is an integer from 1 to 5. The sum of n514’ and n515’ corresponds to n511’. X 52 The R 50 and Y 51 in X 51 are the same as the R 50 and Y 51 in X.

[0100] In formula (X1), the sum of n511 in X 51 and n511’ in X 52 is an integer from 0 to 10, and the sum of n512 in X 51 and n512’ in X 52 is an integer from 0 to 10.

[0101] In one embodiment, formula (X1): -X 51 -CR 51 =CR 52 -X 52 - ···(X1) is the following formula: -[(CR 50 2) n511 -(CH2-Y 51 -(CH2) n54 ) n512 -CR 51 =CR 52 -[(CR 50 2) n511 -(CH2-Y 51 -(CH2) n54 ) n512 - It is represented by. The total value of n511 and n511' in the above formula corresponds to the value of n51 in formula (X), and the total value of n512 and n512' corresponds to the value of n53 in formula (X).

[0102] In one aspect, formula (X1): -X 51 -CR 51 =CR 52 -X 52 - ···(X1) is the following formula: -[-(CR 50 2) n514 -(Y 51 )-(CR 50 2) n515 -CR 51 =CR 52 -[-(CR 50 2) n514’ -(Y 51 )-(CR 50 2) n515’ -]- is represented by. R 50 , Y 51 , n514, n515, R 51 , R 52 , n514’ and n515’ have the same meanings as above respectively. The total value of n514 and n515 corresponds to the value of n511 in formula (X1), and the total value of n514’ and n515’ corresponds to the value of n511’ in formula (X1). The total values of n514, n515, n514’ and n515’ respectively correspond to the value of n51 in formula (X).

[0103] In one aspect, X 51 and X 52 are single bonds. In one aspect, X 51 is -(CR 50 2) n511 -, X 52 is -(CR 50 2) n511’ -, and at least one of n511 and n511’ is an integer of 1 or more. In one aspect, X 51 is -(CR50 2) n511 -(Y 51 ) n512 - represented by, and X 52 are each independently -(CR 50 2) n511’ -(Y 51 ) n512’ - represented by. Any one of n511, n512, n511' and n512' is an integer of 1 or more. In one embodiment, X 51 is represented by -(CR 50 2) n511 -, and X 52 is -(CR 50 2) n511’ -(Y 51 ) n512’ - represented by, and n512' is an integer of 1 or more. In this embodiment, X 52 is -(CR 50 2) n514’ -(Y 51 )-(CR 50 2) n515’ -. In one embodiment, X 51 is -(CR 50 2) n511 -(Y 51 ) n512 - represented by, and X 52 is -(CR 50 2) n511’ - represented by, and n512 is an integer of 1 or more.

[0104] In formula (X2), X 53 is a divalent organic group, -(CR 50 2) n521 -((CH2) n55 -Y 51 -(CH2) n54 ) n522 - represented by. R 50 , n54, n55 and Y 51 are each as defined above. n521 is an integer from 1 to 10, preferably an integer from 1 to 5. n522 is an integer of 1 to 10, and preferably an integer of 1 to 5. The repeating units enclosed in parentheses with n521 or n522 may be present in any order in the formula, and the sum of n521 and n522 is 1 or more.

[0105] Formula (X2) is preferably -(CR 50 2) n524 -((CH2) n55 -Y 51 -(CH2) n54 )-(CR 50 2) n525 - is expressed as n524 is an integer of 0 to 10, and n525 is an integer of 0 to 10, more preferably, n524 is an integer of 0 to 5, and n525 is an integer of 0 to 5. The sum of n524 and n525 corresponds to n521.

[0106] In one embodiment, formula (X2) is -(CR 50 2) n524 -(Y 51 )-(CR 50 2) n525 - is expressed as n524, R 50 , and Y 51 are defined as above. n525 is an integer of 1 to 10, preferably an integer of 1 to 5. For example, n524 is 0 and n525 is an integer of 1 to 5, specifically, n524 is 0 and n525 is an integer of 1 to 3.

[0107] In one embodiment, -X 53 -X 51 -CR 51 =CR 52 -X 52 - is an unsaturated group to which, for example, hydrogen or halogen atoms have been added.

[0108] In one embodiment, X 1 independently at each occurrence, the formula (X'): -CHR 13 -[(CR 50’ 2) n51’ -(CR51 =CR 52 ) n52 -((CH2) n55 -Y 51 -(CH2) n54 ) n53 - ···(X’) is a group represented by R 13 is -OH or -O-(R 14 -O) n4 -R 14’ as represented by R 14 are each independently a C 1-4 alkylene group, preferably CH2 or CH2CH2. n4 are each independently an integer from 0 to 100, preferably an integer from 1 to 50, more preferably an integer from 1 to 40, and even more preferably an integer from 1 to 10. R 14’ are each independently a C 1-4 alkyl group, preferably a C 1-2 alkyl group. R 50’ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, or a C 1-4 alkyl group, preferably a hydrogen atom, a halogen atom, or a C 1-4 alkyl group, and more preferably a hydrogen atom. R 51 、R 52 、Y 51 、n52, and n53 have the same meanings as defined above. n51’ is an integer from 0 to 10, preferably an integer from 0 to 5. The total number of CHR 13 and the number of CR 50’ 2, in other words, 1 + n51’, corresponds to n51 in formula (X). The order of existence of each repeating unit enclosed in parentheses with n51’, n52 or n53 is -[(CR 50’ 2) n51’ -(CR 51 =CR 52 ) n52 -((CH2) n55-Y 51 -(CH2) n54 ) n53 ]- is optional within the structure represented by

[0109] In one embodiment, X 1 teeth, -CHR 13 -[(CR 50’ 2) n516 -((CH2) n55 -Y 51 -(CH2) n54 ) n53 -(CR 50’ 2) n516’ ]- It is expressed as: R 13 , R 50’ , Y 51 , n54, n55, and n53 have the same meanings as above. n516 is an integer of 0 to 10, preferably an integer of 0 to 5, and n516' is an integer of 0 to 10, preferably an integer of 0 to 5. The sum of n516 and n516' corresponds to n51'. In one embodiment, n516 and n516' are each independently an integer of 0 to 10, and n53 is 0. In other words, X 1 Ha-CHR 13 -(CR 50’ 2) n51’ In one embodiment, n516 and n516' are each independently an integer of 1 to 10, and preferably an integer of 1 to 5.

[0110] In one embodiment, X 1 teeth, -CHR 13 -[(CR 50’ 2) n51’ -(CR 51 =CR 52 ) n52 ]- It is expressed as: R 13 , R 50’ , R 51 , R 52 , n51', and n52 have the same meanings as above.

[0111] Not particularly limited to, X 1 Examples of such structures include the following: -(CH2) x1 -CH=CH-(CH2) x2 -(x1 is an integer of 0 to 10, x2 is an integer of 0 to 10, provided that the sum of x1 and x2 is an integer of 0 to 10, preferably x1 is an integer of 0 to 4, and x2 is an integer of 0 to 4, for example, x1 is 0 and x2 is 0, x1 is an integer of 1 to 4 and x2 is 0, x1 is 0 and x2 is an integer of 1 to 4, or x1 is an integer of 1 to 4 and x2 is an integer of 1 to 4), -(CH2) x1 -CH=CH-(CH2) x2 -Ph-(CH2) x3 - (Ph is a phenylene group, x1 is an integer of 0 to 10, x2 is an integer of 0 to 10, and x3 is an integer of 0 to 10, provided that the sum of x1, x2, and x3 is an integer of 0 to 10, preferably x1 is an integer of 1 to 3, x2 is an integer of 0 to 5, and x3 is an integer of 0 to 5, for example, x1 is 1, x2 is 0, and x3 is 0, and in another example, x1 is 1, x2 is 0, and x3 is 1), -CHR 13 -(CH2) x1 -CH=CH-(CH2) x2 -(R 13 is -(OCH2) x11 -CH3 or -(OCH2CH2) x11 -CH3, where x11 is an integer of 1 to 100, x1 is an integer of 0 to 9, and x2 is an integer of 0 to 10, provided that the sum of x1 and x2 is an integer of 0 to 10, preferably x1 is an integer of 0 to 4, and x2 is an integer of 0 to 4, for example, x1 is 0 and x2 is 0, x1 is an integer of 1 to 4 and x2 is 0, x1 is 0 and x2 is an integer of 1 to 4, or x1 is an integer of 1 to 4 and x2 is an integer of 1 to 4). -CHR 13 -(CH2) x1 -CH=CH-(CH2) x2 -Ph-(CH2) x3 -(R 13 is -(OCH2) x11 -CH3 or -(OCH2CH2) x11-CH3, x11 is an integer of 1 to 10; Ph is a phenylene group; x1 is an integer of 0 to 10, x2 is an integer of 0 to 10, and x3 is an integer of 0 to 10, preferably x1 is an integer of 1 to 3, x2 is an integer of 0 to 5, and x3 is an integer of 0 to 5, provided that the sum of x1, x2, and x3 is an integer of 0 to 10. For example, x1 is 1, x2 is 0, and x3 is 0; in another example, x1 is 1, x2 is 0, and x3 is 1), -(CH2) x -(x is an integer of 1 to 10, preferably, x is an integer of 1 to 4), -(CH2) x1 -O-(CH2) x2 -(x1 is an integer between 0 and 10, x2 is an integer between 0 and 10, but the sum of x1 and x2 is an integer between 0 and 10, for example, x1 is 0 and x2 is 0, another example is x1 is 0 and x2 is 1), -(CH2) x1 -Ph-(CH2) x2 - (Ph is a phenylene group; x1 is an integer of 0 to 10, and x2 is an integer of 0 to 10, provided that the sum of x1 and x2 is an integer of 0 to 10, preferably x1 is an integer of 0 to 5, and x2 is an integer of 0 to 5, for example, x1 is an integer of 0 to 3, and x2 is 0, in another example, x1 is an integer of 0 to 3, and x2 is 1), -CHR 13 -(CH2) x -(x is an integer of 0 to 10, preferably, x is an integer of 1 to 4), -CHR 13 -(CH2) x1 -O-(CH2) x2 -(x1 is an integer of 0 to 10, x2 is an integer of 0 to 10, provided that the sum of x1 and x2 is an integer of 0 to 10, preferably x1 is an integer of 0 to 5, and x2 is an integer of 0 to 5, for example, x1 is 1 and x2 is 1), -CHR 13 -(CH2) x1 -Ph--(CH2) x2 - (Ph is a phenylene group; x1 is an integer of 0 to 10, and x2 is an integer of 0 to 10, provided that the sum of x1 and x2 is an integer of 0 to 10, preferably, x1 is an integer of 0 to 5, and x2 is an integer of 0 to 5, for example, x1 is an integer of 0 to 3, and x2 is 0; in another example, x1 is an integer of 0 to 3, and x2 is 1). -CHR 13-(CH2) x1 -CONR 15 -(CH2) x2 -(R 15 is a hydrogen atom, a group having an aromatic ring, a C 1-6 alkyl group, -O-C 1-6 alkyl group or C 3-10 cycloalkyl group, preferably a hydrogen atom; x1 is an integer from 0 to 10, x2 is an integer from 0 to 10, provided that the sum of x1 and x2 is an integer from 0 to 10, preferably, x1 is an integer from 0 to 5, x2 is an integer from 0 to 5, for example, x1 is an integer from 0 to 3, x2 is 0, in another example x1 is an integer from 0 to 3, x2 is 1 to 2, in another example x1 is 0, x2 is 1 to 2). -(CH2) x1 -CONR 15 -(CH2) x2 -(R 15 is a hydrogen atom, a group having an aromatic ring, a C 1-6 alkyl group, -O-C 1-6 alkyl group or C 3-10 cycloalkyl group, preferably a hydrogen atom; x1 is an integer from 0 to 10, x2 is an integer from 0 to 10, provided that the sum of x1 and x2 is an integer from 0 to 10, preferably, x1 is an integer from 0 to 5, x2 is an integer from 0 to 5, for example, x1 is an integer from 0 to 3, x2 is 0, in another example x1 is an integer from 0 to 3, x2 is 1 to 2, in another example x1 is 0, x2 is 1 to 2).

[0112] R Si is, in each occurrence, independently of each other, a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent group containing a Si atom to which a monovalent organic group is bonded, and is represented by the following formula (S1).

Chemical formula

[0113] In formula (S1), X 3 is, in each occurrence, independently of each other, a single bond, an oxygen atom, or a divalent organic group.

[0114] In a preferred embodiment, X 3is a divalent organic group.

[0115] X 3 is preferably C 1-6 Alkylene group, -(CH2) z11 -O-(CH2) z12 - or -(CH2) z13 -phenylene-(CH2) z14 -. This C 1-6 The alkylene group may be straight-chain or branched, but is preferably straight-chain. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted. The above z11 is an integer of 0 to 6, for example, an integer of 1 to 6, and the above z12 is an integer of 0 to 6, for example, an integer of 1 to 6. Preferably, the sum of z11 and z12 is 1 or more. The above z13 is an integer of 0 to 6, for example, an integer of 1 to 6, and the above z14 is an integer of 0 to 6, for example, an integer of 1 to 6. Preferably, the sum of z13 and z14 is 1 or more.

[0116] X 3 is more preferably C 1-6 It can be an alkylene group, for example, -CH2CH2CH2-. In another embodiment, X 3 can be -CH2CH2-.

[0117] R b1 is independently at each occurrence a hydroxyl group or a hydrolyzable group.

[0118] R b1 is preferably, independently at each occurrence, -OR h , -OCOR h , -ON=CR h 2, -NR h 2, -NHR h , —NCO, or halogen (wherein R his a substituted or unsubstituted C 1-4 alkyl group), more preferably -OR h (i.e., an alkoxy group). R h Examples include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group; and substituted alkyl groups such as chloromethyl group. Among them, alkyl groups, especially unsubstituted alkyl groups, are preferred, and methyl group or ethyl group is more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h is an ethyl group.

[0119] R c1 is, in each occurrence, independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above-mentioned hydrolysable group.

[0120] R c1 In, the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, still more preferably a methyl group.

[0121] l1 is, in each occurrence, independently an integer from 0 to 3. However, in each of the formulas (A1) and (A2), at least one l1 is 1. In other words, in R Si , in each of the formulas (A1) and (A2), at least one R b1 exists.

[0122] l1 is preferably, in each occurrence, independently an integer from 1 to 3, more preferably 2 or 3, still more preferably 3.

[0123] Preferably, for each group represented by the formula (S1), at least one R b1 exists. In other words, when R Si is represented by the formula (S1), the terminal R of the formulas (A1) and (A2) SiIn the moiety (hereinafter also simply referred to as the "terminal moiety" of formula (A1) and formula (A2)), there is a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

[0124] Preferably, in the terminal moiety of formula (A1) and the terminal moiety of formula (A2), there are at least two Si atoms to which R b1 is bonded.

[0125] R 11 is, in each occurrence, independently of one another, a hydrogen atom, a benzyl group, a methoxyphenyl group, a benzoyl group, a trityl group, -SiR 71 3, or -(R 72 -O) n7 -R 73 . By having a group represented by -CRSi2(OR 11 ), the wetting spreadability of the composition containing the fluoropolyether group-containing silane compound of the present disclosure with respect to the base material can be improved. The wear resistance of the layer (for example, the surface treatment layer) formed using the composition can be improved.

[0126] R 71 is, independently of one another, a C 1-4 alkyl group, for example, a methyl group. The group represented by -SiR 71 3 is, for example, a trimethylsilyl group.

[0127] R 72 is, independently of one another, a C 1-4 alkylene group, preferably a C 1-2 alkylene group, for example, -CH2CH2-, or -CH2-.

[0128] n7 is, independently of one another, an integer from 1 to 10, preferably an integer from 1 to 6.

[0129] R 73 is, independently of one another, a hydrogen atom, or a monovalent hydrocarbon group which may contain a ring structure. Examples of the monovalent hydrocarbon group containing a ring structure include a monovalent group having an aromatic ring, a cycloalkyl group, or a monovalent hydrocarbon group containing a heterocycloalkyl group. An example of the monovalent group having an aromatic ring is a phenyl group. Examples of the cycloalkyl group include C 3-10 Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Examples of heterocycloalkyl groups include cycloalkyl groups containing an oxygen atom.

[0130] Examples of monovalent hydrocarbon groups containing a ring structure include the following structures. In the following description, -(R 72 -O) n7 - Joins with the right side. [ka]

[0131] R 73 is preferably a hydrogen atom or C 1-4 It is an alkyl group.

[0132] R 73 is preferably C 1-4 alkyl group, more preferably C 1-2 It is an alkyl group.

[0133] Preferably, R 11 is independently in each occurrence a hydrogen atom or -(R 72 -O) n7 -R 73 It is expressed as R 72 , n7 and R 73 are the same as above.

[0134] More preferably, R 11 is independently in each occurrence -CH2O-R 11’ It is expressed as R11’ is a hydrogen atom or a monovalent organic group. Preferably, R 11’ is a hydrogen atom or -(R 72 -O) n7’ -R 73 represented by. R 72 , and R 73 are each as defined above. n7’ is an integer from 0 to 9, preferably an integer from 0 to 5.

[0135] In one embodiment, R 11’ is a hydrogen atom. In one embodiment, R 11’ is -(R 72 -O) n7’ -R 73 represented by the group. In one embodiment, R 11’ is -(R 72 -O) n7’ -R 73 represented by the group, and n7’ is 0.

[0136] (Method for Producing Fluoropolyether Group-Containing Silane Compound) As one embodiment, although not particularly limited, a method suitable for producing the fluoropolyether group-containing silane compound of the present disclosure is described below.

[0137] In one embodiment, the fluoropolyether group-containing silane compound represented by formula (A1) or (A2) of the present disclosure is formula (a27) or formula (a28):

Chemical formula

[0138] The above step (I-1) is preferably carried out in a suitable solvent in the presence of a suitable catalyst.

[0139] The suitable catalyst is not particularly limited, and examples thereof include Pt, Pd, Rh, etc. Such a catalyst may be in any form, for example, in the form of a complex.

[0140] The suitable solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include 1,3-bis(trifluoromethyl)benzene, perfluorobutylethyl ether, perfluorohexylmethyl ether, perfluorohexane, hexafluorobenzene, etc.

[0141] The reaction temperature in such a reaction is not particularly limited, but is usually 0 to 100 °C, preferably 50 to 80 °C. The reaction time is not particularly limited, but is usually 60 to 600 minutes, preferably 120 to 300 minutes. The reaction pressure is not particularly limited, but is -0.2 to 1 MPa (gauge pressure), and is conveniently normal pressure.

[0142] In formula (a27) or formula (a28), R F1 , R F2 has the same meaning as described above, respectively.

[0143] In formula (a27) or formula (a28), -X 6 - corresponds to -X 1 -.

[0144] Preferably, in formula (a27) or formula (a28), -X 6 - is, in each occurrence, independently of each other, -X 61 -CR 61 =CR 62 -X 62 -, or -X 63 - is represented by

[0145] X 61 is a single bond or a divalent organic group, X 62 is a single bond or a divalent organic group, R 61 is a hydrogen atom or a monovalent organic group, R 62 is a hydrogen atom or a monovalent organic group, Each of X 51 X 52 R 51 R 52 corresponds to X 61 can be represented by -(CR 60 2) n611 -((CH2) n614 -Y 61 -(CH2) n613 ) n612 -, X 62 can be represented by -(CR 60 2) n611’ -((CH2) n614’ -Y 61 -(CH2) n613’ ) n612’ -, n611 corresponds to n511, n612 corresponds to n512, n613 corresponds to n54, n614 corresponds to n55, n611’ corresponds to n511’, n612’ corresponds to n512’, n613’ corresponds to n54, n614’ corresponds to n55. The order of existence of each repeating unit enclosed in parentheses with n611 or n612 is arbitrary in the formula. The order of existence of each repeating unit enclosed in parentheses with n611’ or n612’ is arbitrary in the formula. R 60 is R 50 corresponds to Y 61 is Y 51 corresponds to

[0146] X 63 is a divalent organic group and corresponds to X 53 X​63 Each is independently -(CR 60 2) n621 -((CH2) n614 -Y 61 -(CH2) n613 ) n622 - can be represented by n621 corresponds to n521, n622 corresponds to n522, n613 corresponds to n54, and n614 corresponds to n55, respectively; The order of existence of each repeating unit enclosed in parentheses with n621 or n622 attached is arbitrary in the formula.

[0147] In one embodiment, -X 63 - is a product of an addition reaction of a hydrogen atom or a halogen atom to an unsaturated group of -X 61 -CR 61 =CR 62 -X 62 -. This addition reaction can be carried out under normal conditions.

[0148] Z 23 Each independently represents a single bond or a divalent organic group. Z in formula (a27) or (a28) 23 -CH=CH2 corresponds to X in formula (S1) 3

[0149] R 65 is a hydrogen atom or a monovalent organic group. In one embodiment, R 65 is a hydrogen atom. In one embodiment, R 65 is a monovalent organic group.

[0150] In one embodiment, R 65 corresponds to R in formulas (A1) and (A2) 11

[0151] The compound represented by formula (a27) or (a28) is formula (a23) or formula (a24):

Chemical formula

Chemical formula

[0152] In formula (a23), (a24), (a25) and (a26), R F1 , R F2 , X 6 , Z 23 are each as defined above. R 63 is, in each occurrence, independently a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a C 1-4 alkyl group.

[0153] Hal represents a halogen atom, and J represents Mg, Cu, Pd or Zn.

[0154] In addition, when R 65 in formula (a'27) or (a'28) is a monovalent organic group, the compound represented by formula (a'27) or (a'28) can be obtained by reacting the compound represented by formula (a25) or (a26) with, for example, a compound represented by R 65 -Y 62 . Here, Y 62 is a group capable of bonding to R 65 . The above reaction can be carried out using a commonly applicable method. For example, it can be carried out in the presence of a Hunig's base.

[0155] The compound represented by formula (a23) or formula (a24) is a compound represented by formula (a11) or formula (a12):

Chemical formula

[0156] Step (I-3) can be carried out in the presence of a metal-carbene complex having olefin metathesis reaction activity. As the metal-carbene complex, a highly active Grubbs catalyst of the second generation or higher such as the Grubbs second generation catalyst is used. Examples of the Grubbs second generation catalyst include Hoveyda-Grubbus 2nd generation catalyst, Piers second generation metathesis catalyst, nitro-Grela, UltraCat, AquaMet, and UltraNitroCat.

[0157] The above step (I-3) is preferably carried out in an appropriate solvent. ​Suitable solvents are not particularly limited as long as they do not have an adverse effect on the reaction. For example, HCFC-225 (e.g., AsahiKlin AK-225 manufactured by AGC Inc.), 1,3-bis(trifluoromethyl)benzene (mXHF), 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-3,3,3-trifluoro-1-propene, 1,1-dichloro-3,3,3-trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1-propene, 1,1,1,4,4,4-hexafluoro-2-butene, 1,3-bistrifluoromethoxybenzene, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, 3-methoxy-2-(trifluoromethyl)pentane and other fluorine atom-containing solvents; dichloropropane and other fluorine atom-free solvents, etc. can be mentioned, and both fluorine atom-containing solvents and fluorine atom-free solvents may be used.

[0158] The reaction temperature in such a reaction is not particularly limited, but for example, it can be carried out at 0 to 100 °C and can be carried out at room temperature (e.g., 20 to 30 °C). The reaction time is not particularly limited, but is usually 60 to 600 minutes, preferably 120 to 300 minutes, and the reaction pressure is not particularly limited, but is -0.2 to 1 MPa (gauge pressure), and simply it is normal pressure.

[0159] In formulas (a11), (a12), (a21) and (a22), R F1 , R F2 , X 61 , X 62 , R 61 , R 62 , R 63 are each as defined above.

[0160] In one aspect, the fluoropolyether group-containing silane compound of the present disclosure is formula (a31) or formula (a32):

Chemical formula

Chemical formula

Chemical formula

[0161] The compound represented by formula (a31) or formula (a32) can be obtained, for example, by reducing the following formula (a30) or (a30') in the presence of a catalyst. R 64 , and R 64’ are, for example, each independently a C 1-10 alkyl group, or a group having a ring structure formed by bonding to each other, the ring structure having a 5- to 10-membered heterocycle, or a group having a condensed ring formed by bonding to each other, the condensed ring including a 5- to 10-membered heterocycle and a 3- to 10-membered ring other than the heterocycle. R F1 , R F2 , X 61 have the same meanings as described above respectively.

Chemical formula

[0162] The above step can be carried out in a suitable solvent in the presence of a suitable catalyst. The suitable catalyst is not particularly limited, and examples thereof include diisobutylaluminum hydride, lithium aluminum hydride (LAH), etc. The suitable solvent is not particularly limited, and examples thereof include fluorinated solvents such as HFE7200 and HFE7300; non-fluorinated solvents such as THF and diethyl ether; or a mixed solvent containing two or more of these. It is preferable to use a combination of two or more of the above solvents.

[0163] The above process is not particularly limited, and can be carried out, for example, at -78 to 200°C. The reaction time in the above process is not particularly limited, and may be, for example, 0.1 to 168 hours. The reaction pressure in the above process is not particularly limited, and is, for example, 0 to 100 MPa (gauge pressure), and conveniently, it is normal pressure.

[0164] In formulas (a30), (a30’), (a31), (a32), (a33), (a21) and (a22), R F1 , R F2 are each as defined above.

[0165] X 61 , X 62 , R 61 , R 62 , R 63 are each as defined above.

[0166] Through step (II-1), the above step (I-2), and step (I-1), a compound represented by formula (A1) or (A2) of the present disclosure can be formed.

[0167] The present disclosure further provides compounds having the following structures. These compounds are compounds obtained as intermediates in the above production method. By passing through these compounds, the synthesis of the compound represented by formula (A1) or (A2) becomes easier.

[0168] Formula (a23) or formula (a24):

Chemical formula

[0169] In formula (a23) or formula (a24), R F1 , R F2 , R 63 , X 6 are each as defined above.

[0170] Formula (a27) or formula (a28):

Chemical formula

[0171] Although not particularly limited, examples of X 6 in the compound represented by formula (a23), (a24), (a27), or (a28) include the structures described for X 1 .

[0172] (Surface treatment agent) The above-mentioned fluoropolyether group-containing silane compound can be used as a surface treatment agent.

[0173] The surface treatment agent of the present disclosure can contribute to the formation of a surface treatment layer having good ultraviolet durability, water repellency, oil repellency, antifouling property (for example, preventing the adhesion of dirt such as fingerprints), chemical resistance, hydrolysis resistance, suppression effect of slipperiness, high friction durability, heat resistance, moisture resistance, etc.

[0174] In one aspect, the surface treatment agent contains a fluoropolyether group-containing silane compound represented by formula (A1) or formula (A2).

[0175] In one aspect, the surface treatment agent contains at least one selected from the group consisting of a fluoropolyether group-containing silane compound represented by formula (A1) or formula (A2), and a condensate obtained by condensing at least a part of the fluoropolyether group-containing silane compound. Here, the condensate is a partial (hydrolyzed) condensate obtained by condensing the hydroxyl group of the fluoropolyether group-containing silane compound represented by formula (A1) or formula (A2) and / or the hydroxyl group obtained by partially hydrolyzing a hydrolyzable group by a known method. If necessary, a hydrolysis condensation catalyst such as an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium compound (tetra-n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, etc.) may be added to the surface treatment agent. Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly desirable. The addition amount of the hydrolysis condensation catalyst is a catalytic amount, usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, based on 100 parts by mass of the fluoropolyether group-containing silane compound and / or its partial (hydrolyzed) condensate.

[0176] In another aspect, the surface treatment agent of the present disclosure contains a fluoropolyether group-containing silane compound represented by formula (A1) and a fluoropolyether group-containing silane compound represented by formula (A2). The composition (for example, the surface treatment agent) of this aspect can contribute to the formation of a cured layer with good friction durability. The friction durability of the cured layer formed using the composition of this aspect is improved, and the slipperiness on the surface of the cured layer is improved. Also, in the composition of this aspect, the secondary structure of the R F portion is likely to take a helical structure, and the polymer density per unit area and the crosslinking density of the silane coupling agent increase, so it is considered that the strength of the cured layer increases.

[0177] In one aspect, the lower limit of the ratio (molar ratio) of the fluoropolyether group-containing silane compound represented by formula (A2) to the total of the fluoropolyether group-containing silane compound represented by formula (A1) and the fluoropolyether group-containing silane compound represented by formula (A2) contained in the composition (e.g., surface treatment agent) of the present disclosure is preferably 0.001, more preferably 0.002, still more preferably 0.005, even more preferably 0.01, particularly preferably 0.02, and especially preferably 0.05. The upper limit of the ratio (molar ratio) of the fluoropolyether group-containing silane compound represented by formula (A2) to the total of the fluoropolyether group-containing silane compound represented by formula (A1) and the fluoropolyether group-containing silane compound represented by formula (A2) may be preferably 0.70, more preferably 0.60, still more preferably 0.50, further preferably 0.40, even more preferably 0.30, for example 0.20, and specifically 0.10. The ratio (molar ratio) of the fluoropolyether group-containing silane compound represented by formula (A2) to the total of the fluoropolyether group-containing silane compound represented by formula (A1) and the fluoropolyether group-containing silane compound represented by formula (A2) may be 0.001 or more and 0.70 or less, 0.001 or more and 0.60 or less, 0.001 or more and 0.50 or less, 0.002 or more and 0.40 or less, 0.005 or more and 0.30 or less, 0.01 or more and 0.20 or less, for example 0.02 or more and 0.20 or less (specifically 0.15 or less) or 0.05 or more and 0.20 or less (specifically 0.15 or less).

[0178] In one aspect, the lower limit of the ratio (molar ratio) of the fluoropolyether group-containing silane compound represented by formula (A1) to the total of the fluoropolyether group-containing silane compound represented by formula (A1) and the fluoropolyether group-containing silane compound represented by formula (A2) contained in the composition of the present disclosure (for example, a surface treatment agent) is preferably 0.001, more preferably 0.002, still more preferably 0.005, even more preferably 0.01, particularly preferably 0.02, and especially preferably 0.05. The upper limit of the ratio (molar ratio) of the fluoropolyether group-containing silane compound represented by formula (A1) to the total of the fluoropolyether group-containing silane compound represented by formula (A1) and the fluoropolyether group-containing silane compound represented by formula (A2) is preferably 0.70, more preferably 0.60, more preferably 0.50, still more preferably 0.40, even more preferably 0.30, for example, 0.20, specifically 0.10. The ratio (molar ratio) of the fluoropolyether group-containing silane compound represented by formula (A1) to the total of the fluoropolyether group-containing silane compound represented by formula (A1) and the fluoropolyether group-containing silane compound represented by formula (A2) may be 0.001 or more and 0.70 or less, may be 0.001 or more and 0.60 or less, may be 0.001 or more and 0.50 or less, may be 0.002 or more and 0.40 or less, may be 0.005 or more and 0.30 or less, may be 0.01 or more and 0.20 or less, for example, 0.02 or more and 0.20 or less (specifically 0.15 or less) or 0.05 or more and 0.20 or less (specifically 0.15 or less).

[0179] The above surface treatment agent may be diluted with a solvent. Such a solvent is not particularly limited, and examples include: Perfluorohexane, CF3CF2CHCl2, CF3CH2CF2CH3, CF3CHFCHFC2F5, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane ((Zeorola H (trade name), etc.), C4F9OCH3, C4F9OC2H5, CF3CH2OCF2CHF2, C6F 13CH=CH2, C6F 13 OCH3, xylene hexafluoride, perfluorobenzene, methyl pentadecafluoroheptyl ketone, trifluoroethanol, pentafluoropropanol, hexafluoroisopropanol, HCF2CF2CH2OH, methyl trifluoromethanesulfonate, trifluoroacetic acid, and CF3O(CF2CF2O) m1 (CF2O) n1 CF2CF3 [wherein m1 and n1 are each independently an integer of 0 or more and 1000 or less, and the order of existence of each repeating unit enclosed in parentheses with m1 or n1 is arbitrary in the formula, provided that the sum of m1 and n1 is 1 or more.], fluorine atom-containing solvents such as 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-3,3,3-trifluoro-1-propene, 1,1-dichloro-3,3,3-trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1-propene, 1,1,1,4,4,4-hexafluoro-2-butene, etc. can be mentioned. These solvents can be used alone or as a mixture of two or more.

[0180] The water content contained in the above solvent is preferably 20 mass ppm or less. The above water content can be measured using the Karl Fischer method. By having such a water content, the storage stability of the surface treatment agent can be improved.

[0181] In addition to the fluoropolyether group-containing silane compound represented by the formula (A1) or the formula (A2), the surface treatment agent may contain other components. Such other components are not particularly limited, and examples thereof include (non-reactive) fluoropolyether compounds that can be understood as fluorinated oils, preferably perfluoro(poly)ether compounds (hereinafter referred to as "fluorinated oils"), (non-reactive) silicone compounds that can be understood as silicone oils (hereinafter referred to as "silicone oils"), catalysts, lower alcohols, transition metals, halide ions, compounds containing atoms having unshared electron pairs in the molecular structure, and the like.

[0182] The fluorinated oil is not particularly limited, and examples thereof include compounds (perfluoro(poly)ether compounds) represented by the following general formula (1). Rf 5 -(OC4F8) a’ -(OC3F6) b’ -(OC2F4) c’ -(OCF2) d’ -Rf 6 ···(1) In the formula, Rf 5 represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms (preferably a perfluoroalkyl group of C 1―16 ), Rf 6 represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms (preferably a C 1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom, and Rf 5 and Rf 6 are more preferably each independently a C 1-3 perfluoroalkyl group. a', b', c' and d' each represent four repeating unit numbers of perfluoro(poly)ether that constitute the main skeleton of the polymer, and are each an integer of 0 or more and 300 or less, independent of each other. 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. The repeating unit has at least 1 branched structure. That is, the repeating unit has at least 1 CF3 terminal (specifically, -CF3, -C2F5, etc., more specifically -CF3). Examples of the repeating unit having a branched structure include -(OC4F8)- such as -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)- and -(OCF2CF(C2F5))-; -(OC3F6)- such as -(OCF(CF3)CF2)- and -(OCF2CF(CF3))-; -(OC2F4)- such as -(OCF(CF3))-.

[0183] Examples of the perfluoro(poly)ether compound represented by the above general formula (1) include compounds (which may be one or more mixtures) represented by any of the following general formulas (1a) and (1b). Rf 5 -(OCF(CF3)CF2) b’’ -Rf 6 ···(1a) Rf 5 -(OC4F8) a’’ -(OC3F6) b’’ -(OCF(CF3)) c’’ -(OCF2) d’’ -Rf 6 ···(1b) In these formulas, Rf 5 and Rf 6is as described above; in formula (1a), b’’ is an integer of 1 or more and 100 or less; in formula (1b), a’’ and b’’ are each independently an integer of 1 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 existence of each repeating unit enclosed in parentheses with subscripts a’’, b’’, c’’, d’’ is arbitrary in the formula. -(OC4F8)- 、 -(OC3F6)- has a branched structure.

[0184] The fluorine-containing oil may have a number average molecular weight of 1,000 to 30,000. In particular, the number average molecular weight of the compound represented by formula (1a) is preferably 2,000 to 8,000. By having such a number average molecular weight, good friction durability can be obtained. In one aspect, the number average molecular weight of the compound represented by formula (1b) is 3,000 to 8,000. In another aspect, the number average molecular weight of the compound represented by formula (1b) is 8,000 to 30,000.

[0185] In the above surface treatment agent, the fluorine-containing oil may be contained, for example, in an amount of 0 to 500 parts by mass, preferably 0 to 100 parts by mass, more preferably 1 to 50 parts by mass, and still more preferably 1 to 5 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing silane compound.

[0186] In the above surface treatment agent, the fluorine-containing oil may be contained, for example, in an amount of 0 to 30 mol%, preferably 0 to 20 mol%, more preferably 0 to 10 mol%, based on the total amount of the fluoropolyether group-containing silane compound and the fluorine-containing oil.

[0187] Also, from another perspective, the fluorine-containing oil may be a compound represented by the general formula Rf’-F (wherein Rf’ is a C 5-16 perfluoroalkyl group).) It may also be a chlorotrifluoroethylene oligomer. The compound represented by Rf’-F and the chlorotrifluoroethylene oligomer are such that Rf is C 1-16It is preferable in that a high affinity can be obtained with the perfluoro( poly) ether group-containing silane compound which is a perfluoroalkyl group.

[0188] The fluorine-containing oil contributes to improving the surface slipperiness of the surface treatment layer.

[0189] In one aspect, the surface treatment agent of the present disclosure contains a compound represented by formula (A1) and a fluorine-containing oil.

[0190] In one aspect, the surface treatment agent of the present disclosure contains a compound represented by formula (A2) and a fluorine-containing oil.

[0191] In one aspect, the surface treatment agent of the present disclosure contains a compound represented by formula (A1), a compound represented by formula (A2), and a fluorine-containing oil.

[0192] In one aspect, with respect to the total of the compound represented by formula (A1), the compound represented by formula (A2), and the fluorine-containing oil, the compound represented by formula (A2) is preferably contained in an amount of 0.001 to 70 mol%, and the fluorine-containing oil is preferably contained in an amount of 0.001 to 50 mol%. More preferably, the compound represented by formula (A2) is contained in an amount of 0.01 to 60 mol%, and the fluorine-containing oil is contained in an amount of 0.01 to 40 mol%. Even more preferably, the compound represented by formula (A2) is contained in an amount of 0.1 to 50 mol%, and the fluorine-containing oil is contained in an amount of 0.1 to 30 mol%.

[0193] In one aspect, with respect to the total of the compound represented by formula (A1), the compound represented by formula (A2), and the fluorine-containing oil, the compound represented by formula (A1) is preferably contained in an amount of 0.001 to 70 mol%, and the fluorine-containing oil is preferably contained in an amount of 0.001 to 50 mol%. More preferably, the compound represented by formula (A1) is contained in an amount of 0.01 to 60 mol%, and the fluorine-containing oil is contained in an amount of 0.01 to 40 mol%. Even more preferably, the compound represented by formula (A1) is contained in an amount of 0.1 to 50 mol%, and the fluorine-containing oil is contained in an amount of 0.1 to 30 mol%.

[0194] 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 the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying a straight silicone oil with an alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, or the like. Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.

[0195] In the above surface treatment agent, such a silicone oil can be contained in an amount of, for example, 0 to 50 parts by mass, preferably 0 to 5 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing silane compound (in the case of two or more kinds, the total thereof, the same applies hereinafter).

[0196] The silicone oil contributes to improving the surface slipperiness of the surface treatment layer.

[0197] Examples of the catalyst include acids (such as acetic acid, trifluoroacetic acid, etc.), bases (such as ammonia, triethylamine, diethylamine, etc.), transition metals (such as Ti, Ni, Sn, etc.).

[0198] The catalyst promotes the hydrolysis and dehydration condensation of the above-mentioned fluorine-containing silane compound and promotes the formation of the surface treatment layer.

[0199] Examples of the lower alcohol as the other component include alcohol compounds having 1 to 6 carbon atoms.

[0200] Examples of the transition metal include platinum, ruthenium, rhodium, etc.

[0201] Examples of the halide ion include chloride ion.

[0202] Examples of the compound containing an atom having a non-bonding electron pair in the molecular structure include diethylamine, triethylamine, aniline, pyridine, hexamethylphosphoramide, N,N-diethylacetamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylformamide, N,N-dimethylformamide, N-methylpyrrolidone, tetramethylurea, dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, methyl phenyl sulfoxide, diphenyl sulfoxide, and the like. Among these compounds, it is preferable to use dimethyl sulfoxide or tetramethylene sulfoxide.

[0203] Examples of other components include, in addition to the above, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.

[0204] In one aspect, the surface treatment agent does not contain a fluorine-containing oil, a silicone oil, a catalyst, a lower alcohol, a transition metal, a halide ion, or a compound containing an atom having a non-bonding electron pair in the molecular structure, which are the other components described above.

[0205] In one aspect, with respect to the total of the compound represented by formula (A1), the compound represented by formula (A2), and the fluorine-containing oil, the compound represented by formula (A2) may be contained, for example, in an amount of 70 mol% or less, 60 mol% or less, 50 mol% or less, 0.001 mol% or more, 0.01 mol% or more, or 0.1 mol% or more. With respect to the total of the compound represented by formula (A1), the compound represented by formula (A2), and the fluorine-containing oil, the compound represented by formula (A2) may be contained, for example, in an amount of 1 to 70 mol% or 5 to 50 mol%.

[0206] In one aspect, the composition (e.g., surface treatment agent) of the present disclosure contains a compound represented by formula (A1), a compound represented by formula (A2), and a fluorinated oil. In this aspect, with respect to the total of the compound represented by formula (A1), the compound represented by formula (A2), and the fluorinated oil, the fluorinated oil may be contained, for example, in an amount of 0.001 mol% or more, 0.01 mol% or more, 1.0 mol% or more, 50 mol% or less, 40 mol% or less, 30 mol% or less, or 10 mol% or less. With respect to the total of the compound represented by formula (A1), the compound represented by formula (A2), and the fluorinated oil, the fluorinated oil may be contained, for example, in an amount of 0.001 to 50 mol% or 0.01 to 40 mol%. In this aspect, with respect to the total of the compound represented by formula (A1), the compound represented by formula (A2), and the fluorinated oil, it is preferable that the compound represented by formula (A2) is contained in an amount of 0.001 to 70 mol% and the fluorinated oil is contained in an amount of 0.001 to 50 mol%. More preferably, the compound represented by formula (A2) is contained in an amount of 0.01 to 60 mol% and the fluorinated oil is contained in an amount of 0.01 to 40 mol%. Even more preferably, the compound represented by formula (A2) is contained in an amount of 0.1 to 50 mol% and the fluorinated oil is contained in an amount of 0.1 to 30 mol%. The composition (e.g., surface treatment agent) of this aspect can contribute to the formation of a cured layer with good friction durability. Furthermore, the friction durability of the cured layer formed using the composition of this aspect is improved, and the slipperiness on the surface of the cured layer is improved. Also, in the composition of this aspect, the secondary structure of the R F portion is likely to take a helical structure, and the polymer density per unit area and the crosslink density of the silane coupling agent increase, so it is considered that the strength of the cured layer increases.

[0207] In one aspect, the composition (e.g., surface treatment agent) of the present disclosure contains a compound represented by formula (A1), a compound represented by formula (A2), and a fluorinated oil. In this embodiment, with respect to the total of the compound represented by formula (A1) and the compound represented by formula (A2), the compound represented by formula (A2) may be contained in an amount of 0.001 mol% or more and less than 50 mol%, may be contained in an amount of 0.1 mol% or more and less than 50 mol%, may be contained in an amount of 1 mol% or more and less than 50 mol%, for example, may be contained in an amount of 10 mol% or more and less than 50 mol%.

[0208] In one embodiment, the composition (for example, the surface treatment agent) of the present disclosure contains a compound represented by formula (A1), a compound represented by formula (A2), and a fluorinated oil. In this embodiment, with respect to the total of the compound represented by formula (A1) and the compound represented by formula (A2), the compound represented by formula (A1) may be contained in an amount of 0.001 mol% or more and less than 50 mol%, may be contained in an amount of 0.1 mol% or more and less than 50 mol%, may be contained in an amount of 10 mol% or more and less than 50 mol%, for example, may be contained in an amount of 20 mol% or more and less than 50 mol%, or may be contained in an amount of 30 mol% or more and less than 50 mol%.

[0209] In one embodiment, the composition (for example, the surface treatment agent) of the present disclosure contains a compound represented by formula (A1), a compound represented by formula (A2), and a fluorinated oil. In this embodiment, with respect to the total of the compound represented by formula (A1) and the compound represented by formula (A2), the compound represented by formula (A2) may be contained in an amount of 35 mol% or more and less than 65 mol%, or may be contained in an amount of 40 mol% or more and less than 60 mol%.

[0210] In one embodiment, the surface treatment agent of the present disclosure contains a fluoropolyether group-containing silane compound represented by formula (A1) or formula (A2), and does not contain a fluorinated oil which is the other component described above (for example, the content of the fluorinated oil is 1 part by mass or less with respect to 100 parts by mass of the surface treatment agent, and more specifically, is 0 part by mass).

[0211] The composition of the present disclosure can be used as a surface treatment agent for surface treatment of a substrate.

[0212] The surface treatment agent of the present disclosure can be impregnated into a porous material, for example, a porous ceramic material, or a metal fiber such as steel wool solidified in a cotton-like form, to form pellets. The pellets can be used, for example, in vacuum deposition.

[0213] (Article) Hereinafter, the article of the present disclosure will be described.

[0214] The article of the present disclosure includes a substrate and a layer (surface treatment layer) formed from the surface treatment agent containing the fluoropolyether group-containing silane compound or the fluoropolyether group-containing silane compound of the present disclosure on the surface of the substrate (hereinafter, these are simply referred to as "the surface treatment agent of the present disclosure" for the sake of simplicity).

[0215] The substrate that can be used in the present disclosure can be composed of any suitable material, for example, glass, resin (natural or synthetic resin, which may be a general plastic material and may be in the form of a plate, film, or other forms), metal, ceramics, semiconductor (such as silicon, germanium, etc.), fiber (such as woven fabric, non-woven fabric, etc.), fur, leather, wood, porcelain, stone, etc., building members, etc.

[0216] For example, when the article to be manufactured is an optical member, the material constituting the surface of the base material may be a material for an optical member, such as glass or transparent plastic. Further, when the article to be manufactured is an optical member, some layer (or film), such as a hard coat layer or an antireflection layer, may be formed on the surface (outermost layer) of the base material. For the antireflection layer, either a single-layer antireflection layer or a multilayer antireflection layer may be used. Examples of inorganic substances that can be used for the antireflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, and the like. These inorganic substances may be used alone or in combination of two or more thereof (for example, as a mixture). When forming a multilayer antireflection layer, it is preferable to use SiO2 and / or SiO for its outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, may be provided on a part of the surface of the base material (glass). Further, depending on its specific specifications and the like, the base material may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), a matte film layer, a hard coating film layer, a polarizing film, a retardation film, and a liquid crystal display module, and the like.

[0217] The shape of the base material is not particularly limited. Further, the surface region of the base material on which the layer formed by the surface treatment agent of the present disclosure is to be formed may be at least a part of the surface of the base material, and can be appropriately determined according to the use and specific specifications of the article to be manufactured.

[0218] As such a substrate, at least its surface portion may be made of a material originally having a hydroxyl group. Examples of such materials include glass, and metals (especially base metals), ceramics, semiconductors, etc. on which a natural oxide film or a thermal oxide film is formed on the surface. Alternatively, when it is not sufficient to have a hydroxyl group, such as in the case of a resin, or when it originally does not have a hydroxyl group, by subjecting the substrate to some pretreatment, hydroxyl groups can be introduced or increased on the surface of the substrate. Examples of such pretreatment include plasma treatment (e.g., corona discharge) and ion beam irradiation. Plasma treatment can be suitably used not only to introduce or increase hydroxyl groups on the substrate surface but also to clean the substrate surface (remove foreign substances, etc.). Another example of such pretreatment is a method in which an interfacial adsorbent having a carbon-carbon unsaturated bond group is formed in the form of a monomolecular film on the substrate surface in advance by the LB method (Langmuir-Blodgett method) or chemisorption method, and then the unsaturated bond is cleaved in an atmosphere containing oxygen, nitrogen, etc.

[0219] Or alternatively, as such a substrate, at least its surface portion may be made of a material containing a silicone compound having one or more other reactive groups, such as Si-H groups, or an alkoxysilane.

[0220] Next, a layer of the surface treatment agent of the present disclosure is formed on the surface of such a substrate, and this layer is post-treated as necessary, thereby forming a layer from the surface treatment agent of the present disclosure.

[0221] The formation of the layer of the surface treatment agent of the present disclosure can be carried out by applying the above surface treatment agent to the surface of the substrate so as to cover the surface. The coating method is not particularly limited. For example, wet coating methods and dry coating methods can be used.

[0222] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and similar methods.

[0223] Examples of dry coating methods include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum vapor deposition methods) 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.

[0224] Furthermore, coating by an atmospheric pressure plasma method is also possible.

[0225] When using a wet coating method, the surface treatment agent of the present disclosure can be diluted with a solvent and then applied to the substrate surface. From the viewpoints of the stability of the surface treatment agent of the present disclosure and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (for example, bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (for example, C6F 13CH2CH3 (e.g., Asahiklin (registered trademark) AC-6000 manufactured by AGC Corporation), 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), and 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 AGC Corporation). These solvents can be used alone or as a mixture of two or more. Among these, hydrofluoroethers are preferred, with perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) being particularly preferred.

[0226] 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.

[0227] The formation of the layer of the surface treatment agent is preferably carried out such that the surface treatment agent of the present disclosure is present in the layer together with a catalyst for hydrolysis and dehydration condensation. For simplicity, in the case of the wet coating method, after diluting the surface treatment agent of the present disclosure with a solvent, a catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure immediately before applying it to the substrate surface. In the case of the dry coating method, the surface treatment agent of the present disclosure added with a catalyst may be directly subjected to vapor deposition (usually vacuum vapor deposition), or vapor deposition (usually vacuum vapor deposition) may be carried out using a pellet-like substance impregnated with the surface treatment agent of the present disclosure added with a catalyst on a metal porous body such as iron or copper.

[0228] Any suitable acid or base can be used as the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid, etc. can be used. Also, as the base catalyst, for example, ammonia, organic amines, etc. can be used.

[0229] As described above, a layer derived from the surface treatment agent of the present disclosure is formed on the surface of the substrate, and the article of the present disclosure is manufactured. The layer thus obtained has both high surface slipperiness and high friction durability. In addition to high friction durability, the layer may also have water repellency, oil repellency, antifouling properties (e.g., preventing the adhesion of dirt such as fingerprints), waterproof properties (preventing the intrusion of water into electronic components, etc.), surface slipperiness (or lubricity, e.g., the wiping property of dirt such as fingerprints and the excellent tactile sensation against fingers), etc., depending on the composition of the surface treatment agent used, and can be suitably used as a functional thin film.

[0230] That is, the present disclosure further relates to an optical material having a layer derived from the surface treatment agent of the present disclosure as the outermost layer.

[0231] As the optical material, in addition to the optical materials for displays and the like exemplified below, a wide variety of optical materials are preferably mentioned: for example, 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, fluorescent display tubes (VFDs), field emission displays (FEDs; Field Emission Displays), etc., or protection plates for these displays, or those with an antireflection film treatment on their surfaces.

[0232] The article having the layer obtained by the present disclosure is not particularly limited, but may be an optical member. Examples of the optical member include the following: lenses such as glasses; front protection plates, antireflection plates, polarizing plates, and antiglare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disk surfaces of optical disks such as Blu-ray (registered trademark) disks, DVD disks, CD-Rs, and MOs; optical fibers; display surfaces of watches, etc.

[0233] Also, the article having the layer obtained by the present disclosure may be an interior or exterior automotive member. Examples of the exterior material include the following: windows, light covers, and exterior camera covers. Examples of the interior material include the following: instrument panel covers, navigation system touch panels, and decorative interior materials.

[0234] Also, the article having the layer obtained by the present disclosure may be a medical device or a medical material.

[0235] The thickness of the above layer is not particularly limited. In the case of an optical member, it is preferable from the viewpoints of optical performance, surface slipperiness, friction durability, and antifouling property that the thickness of the above layer is in the range of 1 to 50 nm, 1 to 30 nm, preferably 1 to 15 nm.

[0236] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims.

Example

[0237] Hereinafter, it will be described more specifically through examples, but the present disclosure is not limited to these examples. In this example, all the chemical formulas shown below represent average compositions, and the order of existence of the repeating units constituting the perfluoropolyether is arbitrary.

[0238] (Example 1) CF3O-(CF2CF2O) n -(CF2O) m 4 g (1.0 mmol) of the terminal allyl compound represented by -CF2CH2CH=CH2 (n = 22, m = 22) was dissolved in 8.0 mL of AK-225, and then 0.5 g of methyl butenoate and 42 mg of Grubbs catalyst (second generation) were added. After stirring overnight at room temperature, it was washed with chloroform and then concentrated to dryness. The composition obtained by concentration to dryness was purified by a silica gel column to obtain 2.1 g of Compound 1-1. (Compound 1-1)

Chemical formula

[0239] After dissolving 2.1 g of Compound 1-1 in 10.0 mL of 2,2,3,3,3-pentafluoro-1-propanol, 0.5 g of palladium on activated carbon suspended in 3.0 mL of formic acid and 1.0 mL of water was added, and the mixture was stirred overnight at room temperature. Subsequently, after filtration through celite, it was concentrated to dryness and purified by silica gel column chromatography to obtain 1.73 g of Compound 1-2. (Compound 1-2)

Chem.

[0240] 1.72 g of Compound 1-2 was dissolved in 5.0 mL of HFE7200, cooled to 0 °C, and then 1.84 mL of allylmagnesium bromide (about 13% ethyl ether solution, about 0.7 mol / L) was added dropwise. After the addition, it was stirred until the next morning. Subsequently, hydrochloric acid was added to the reaction solution and stirred, and then the hydrochloric acid phase was removed by liquid separation and washed with water. Subsequently, it was washed with acetone, concentrated to dryness, and purified by silica gel column chromatography to obtain 1.09 g of Compound 1-3. (Compound 1-3)

Chem.

[0241] After dissolving 0.53 g of Compound 1-3 in 5.0 mL of AK-225, 0.16 mL of Hunig's base was added. Subsequently, 75.0 μL of methoxyethoxymethyl chloride was added, and the mixture was stirred at 35 °C for 4 days. Subsequently, it was washed with methanol and acetone and concentrated to dryness to obtain 0.54 g of Compound 1-4. (Compound 1-4)

Chemical Structure

[0242] After dissolving 0.56 g of Compound 1-4 in 1.5 mL of HFE7200, 40.0 μL of Karlstedt's catalyst and 6.0 μL of aniline were added in sequence. After stirring at room temperature for 30 minutes, 0.2 mL of trimethoxysilane was added, and the mixture was stirred at room temperature for 3 hours. After filtration and concentration to dryness, 0.56 g of Compound 1-5 was obtained. (Compound 1-5)

Chemical Structure

[0243] (Example 2) After dissolving 0.507 g of Compound 1-3 in 5.0 mL of AK-225, 0.304 mL of Hunig's base was added. Subsequently, 80.0 μl of methoxymethyl chloride was added, and the mixture was stirred at 35 °C for 5 days. Subsequently, it was washed with methanol, acetone, and chloroform. After concentration to dryness, purification by silica gel column chromatography gave 0.51 g of Compound 2-1. (Compound 2-1) [Chemical formula] 1 H NMR (mXHF, 400 MHz) δ: 1.80 - 2.00 (m, 6 H), 2.40 - 2.50 (m, 2 H), 2.65 - 2.70 (m, 4 H), 3.69 (s, 3 H), 5.05 (s, 2 H), 5.30 - 5.45 (m, 4 H), 6.15 - 6.25 (m, 2 H); 19 F NMR (mXHF, 400 MHz) δ: -53.9, -54.2, -55.7, -56.5, -57.5, -58.3, -58.5, -60.0, -72.3, -74.5, -83.5, -86.0, -87.7, -91.1, -93.1.

[0244] After dissolving 0.58 g of Compound 2-1 in 2.0 mL of HFE7200, 40.0 μl of Karlstedt's catalyst and 7.0 μl of aniline were added. After stirring at room temperature for 30 minutes, 0.2 mL (1.57 mmol) of trimethoxysilane was added, and the mixture was stirred at room temperature for 2.5 hours. After filtration and concentration to dryness, 0.59 g of Compound 2-2 was obtained. (Compound 2-2) [Chemical formula] 11H NMR (mXHF, 400 MHz) δ: 0.95 - 1.10 (m, 4 H), 1.85 - 2.10 (m, 8 H), 1.70 - 2.10 (m, 14 H), 2.40 - 2.60 (m, 2 H), 3.70 (s, 3 H), 3.85 - 4.20 (s, 18 H), 5.01 (s, 2 H); 19 19F NMR (mXHF, 400 MHz) δ: -53.9, -54.2, -55.8, -57.5, -58.2, -58.3, -60.0, -72.3, -74.4, -83.5, -86.0, -87.7, -91.1, -92.8, -93.3.

[0245] (Example 3) CF3O-(CF2CF2O) n -(CF2O) m 2 g of the terminal allyl compound represented by -CF2CH2CH=CH2 (n = 22, m = 22) was dissolved in 3.0 mL of AK - 225, and then 0.544 mL of ethyl acrylate and 21 mg of Grubbs catalyst (second generation) were added. After stirring overnight at room temperature, it was washed with chloroform and concentrated to dryness. By purification with a silica gel column, 1.86 g of Compound 3 - 1 was obtained. (Compound 3 - 1) [Chemical formula] 1 1H NMR (mXHF, 400 MHz) δ: 1.60 (t, 3 H), 3.15 - 3.35 (m, 2 H), 4.40 - 4.52 (m, 2 H), 6.30 - 6.50 (m, 1 H), 7.20 - 7.30 (m, 1 H); 19 19F NMR (mXHF, 400 MHz) δ: -54.2, -55.8, -56.5, -57.5, -58.1, -58.3, -60.0, -71.8, -73.9, -74.7, -76.1, -83.5, -86.0, -87.7, -91.1, -93.1.

[0246] After dissolving 1.83 g of Compound 3-1 in 12.0 mL of 2,2,3,3,3-pentafluoro-1-propanol, a suspension of 0.3 g of palladium on activated carbon in 4.0 mL of formic acid and 1.0 mL of water was added, and the mixture was stirred at room temperature overnight. Subsequently, after filtration through celite and concentration to dryness, 1.69 g of Compound 3-2 was obtained. (Compound 3-2)

Chemical Structure

[0247] After dissolving 1.69 g of Compound 3-2 in 4.0 mL of HFE7200, the solution was cooled to 0 °C, and 1.81 mL of allylmagnesium bromide (approx. 13% ethyl ether solution, approx. 0.7 mol / L) was added dropwise. After the addition, the mixture was stirred until the next morning. Hydrochloric acid was added to the reaction solution and stirred, and then the hydrochloric acid layer was removed by liquid separation and washed with water. Subsequently, it was washed with methanol and chloroform, and after concentration to dryness, 1.69 g of Compound 3-3 was obtained. (Compound 3-3)

Chemical Structure

[0248] After dissolving 0.62 g of Compound 3-3 in 1.2 mL of HFE7200, 35.0 μL of Karlstedt catalyst and 5.6 μL of aniline were added. After stirring at room temperature for 30 minutes, 0.138 mL of trimethoxysilane was added and the mixture was stirred at room temperature for 3 hours. Subsequently, it was washed with chloroform and concentrated to dryness to obtain 0.64 g of Compound 3-4. (Compound 3-4)

Chemical formula

[0249] (Example 4) After dissolving 0.577 g of Compound 3-3 in 2.0 mL of AK-225, 148.0 μL of Hunig's base was added. Subsequently, 46.0 μL of methoxymethyl chloride was added and the mixture was stirred at 37 °C for two nights. Subsequently, it was washed with methanol, acetone, and chloroform. After concentration to dryness, it was purified by silica gel column to obtain 0.554 g of Compound 4-1. (Compound 4-1)

Chemical formula

[0250] After dissolving 0.554 g of Compound 4-1 in 1.0 mL of HFE7200, 35.0 μL of a Karl Fischer catalyst and 5.6 μL of aniline were added. After stirring at room temperature for 30 minutes, 88.0 μL of trimethoxysilane was added, and the mixture was stirred at room temperature for 2.5 hours. After filtration and concentration to dryness, 0.59 g of Compound 4-2 was obtained. (Compound 4-2) [Chemical formula] 1 1H NMR (mXHF, 400 MHz) δ: 0.95-1.10 (m, 4 H), 1.80-2.05 (m, 12 H), 1.70-2.10 (m, 14 H), 2.30-2.50 (m, 2 H), 3.70 (s, 3 H), 3.85-4.20 (s, 18 H), 5.01 (s, 2 H); 19 19F NMR (mXHF, 400 MHz) δ: -53.8, -54.0, -56.0, -56.5, -57.5, -58.2, -58.3, -60.0, -72.5, -74.8, -83.5, -86.0, -87.8, -91.0, -92.8, -93.2.

[0251] (Example 5) CF3O-(CF2CF2O) n -(CF2O) m After dissolving 5.32 g of the terminal allyl compound represented by -CF2CH2CH=CH2 (n = 22, m = 22) in 25.0 mL of AK-225, 1.89 mL of ethyl pentenoate and 0.113 g of a Grubbs catalyst (second generation) were added. After stirring overnight at 35 °C, the mixture was washed with acetone and chloroform and then concentrated to dryness. After purification by silica gel column chromatography, 2.71 g of Compound 5-1 was obtained. (Compound 5-1) [Chemistry] 1 H NMR (mXHF, 400 MHz) δ: 1.53 (t, 3 H), 2.60 - 2.80 (m, 4 H), 3.00 - 3.20 (m, 2 H), 4.40 - 4.50 (m, 2 H), 5.70 - 5.90 (m, 1 H), 6.00 - 6.10 (m, 1 H).

[0252] 2.7 g of compound 5 - 1 was dissolved in 10.0 mL of 2,2,3,3,3 - pentafluoro - 1 - propanol. Then, a suspension of 0.3 g of palladium - on - activated carbon in 2.0 mL of formic acid and 1.0 mL of water was added, and the mixture was stirred overnight at room temperature. Subsequently, it was filtered, concentrated to dryness, and washed with saturated aqueous sodium hydrogen carbonate solution and water. After drying over Na2SO4, it was filtered and concentrated to dryness to obtain 2.58 g of compound 5 - 2. (Compound 5 - 2) [Chemistry] 1 H NMR (mXHF, 400 MHz) δ: 1.54 (t, 3 H), 1.65 - 1.80 (m, 2 H), 1.85 - 2.10 (m, 4 H), 2.30 - 2.50 (m, 2 H), 2.55 - 2.65 (m, 2 H), 4.40 - 4.50 (m, 2 H); 19 F NMR (mXHF, 400 MHz) δ: - 54.0, - 54.2, - 55.8, - 56.4, - 57.3, - 58.1, - 58.2, - 60.0, - 72.4, - 74.5, - 85.9, - 87.4, - 91.2, - 92.8, - 93.3.

[0253] After dissolving 2.58 g of Compound 5-2 in 4.0 mL of HFE7200, the solution was cooled to 0 °C, and 2.3 mL of allylmagnesium bromide (approx. 13% ethyl ether solution, approx. 0.7 mol / L) was added dropwise. After the addition, the mixture was stirred until the next morning. Hydrochloric acid was added to the reaction solution and stirred. The hydrochloric acid layer was removed by liquid separation, and the residue was washed with water, methanol, and acetone, concentrated to dryness, and purified by silica gel column chromatography to obtain 2.24 g of Compound 5-3. (Compound 5-3)

Chem.

[0254] After dissolving 0.42 g of Compound 5-3 in 1.1 mL of HFE7200, 25.0 μL of Karl Fischer catalyst and 4.0 μL of aniline were added. The mixture was stirred at room temperature for 30 minutes, then 0.1 mL of trimethoxysilane was added, and the mixture was stirred at room temperature for 3.5 hours. After filtration and concentration to dryness, 0.44 g of Compound 5-4 was obtained. (Compound 5-4)

Chem.

[0255] (Example 6) Dissolve 0.668 g of Compound 5-3 in 3.0 mL of AK-225, then add 0.17 mL of Hunig's base, DMAP, and 50.0 μL of methoxymethyl chloride, and stir at a bath temperature of 35 °C for 4 days. Subsequently, after concentrating the reaction solution to dryness, purify it by silica gel column to obtain 0.56 g of Compound 6-1. (Compound 6-1) [Chemical formula] 1 1H NMR (mXHF, 400 MHz) δ: 1.50 - 2.10 (m, 8 H), 2.35 - 2.50 (m, 2 H), 2.60 - 2.70 (m, 4 H), 3.70 (s, 3 H), 5.05 (s, 2 H), 5.35 - 5.45 (m, 4 H), 6.15 - 6.30 (m, 2 H); 19 19F NMR (mXHF, 400 MHz) δ: -53.9, -54.2, -55.8, -56.4, -57.5, -58.1, -58.3, -60.0, -72.3, -74.4, -85.8, -87.5, -91.1, -92.8, -93.3.

[0256] Dissolve 0.56 g of Compound 6-1 in 1.1 mL of HFE7200, then add 24.7 μL of Karlstedt catalyst and 4.0 μL of aniline. After stirring at room temperature for 30 minutes, add 98.7 μL of trimethoxysilane and stir at room temperature for 3.5 hours. After filtration and concentration to dryness, 0.57 g of Compound 6-2 was obtained. (Compound 6-2) [Chemical formula] 11H NMR (mXHF, 400 MHz) δ: 0.95 - 1.10 (m, 4 H), 1.60 - 2.10 (m, 8 H), 1.70 - 2.10 (m, 16 H), 2.35 - 2.51 (m, 2 H), 3.71 (s, 3 H), 3.80 - 4.15 (s, 18 H), 5.02 (s, 2 H); 19 19F NMR (mXHF, 400 MHz) δ: -53.9, -54.2, -55.8, -56.4, -57.5, -58.1, -58.3, -60.0, -72.3, -74.5, -86.0, -87.7, -91.2, -92.8, -93.3.

[0257] (Example 7) 3.45 g of β - propiolactone was dissolved in 10.0 mL of methanol, and then 0.53 g of sodium methoxide was added. After stirring at 50 °C for one and a half hours, it was concentrated to dryness. Diethyl ether and water were added to the composition obtained by concentration to dryness, followed by liquid - liquid separation and concentration to dryness to obtain 2.2 g of compound 7 - 1. (Compound 7 - 1) [Chemical formula] 1 1H NMR (CDCl3, 400 MHz) δ: 1.60 - 1.85 (m, 7 H), 1.90 - 2.00 (m, 2 H), 2.35 - 2.45 (m, 2 H), 2.56 - 2.90 (m, 2 H), 3.72 (s, 3 H), 3.87 (m, 2 H)

[0258] 2.2 g of compound 7 - 1 was dissolved in 15.0 mL of N,N - dimethylformamide (DMF) and cooled in an ice bath. After 10 minutes, 1.73 g of imidazole and 3.82 g of tert - butyldimethylsilyl chloride were added in sequence, and the mixture was stirred until the next morning. Diethyl ether and water were added to the reaction solution, followed by liquid - liquid separation. After concentration to dryness, column purification was carried out to obtain 2.81 g of compound 7 - 2. (Compound 7 - 2) [Chemical formula] 1 1H NMR (CDCl3, 400 MHz) δ: 0.04 (s, 6 H), 0.86 (s, 9 H), 2.35 - 2.45 (m, 2 H), 2.52 (t, 2 H), 3.67 (s, 3 H), 3.88 (t, 2 H)

[0259] After dissolving 2.71 g of Compound 7 - 2 in 8.0 mL of tetrahydrofuran (THF), it was cooled in an ice bath. After 10 minutes, 39 mL of allylmagnesium bromide was added, and the mixture was stirred until the next morning. Diethyl ether and an aqueous ammonium chloride solution were added to the reaction solution, followed by liquid separation. After concentration to dryness, column purification was performed to obtain 2.25 g of Compound 7 - 3. (Compound 7 - 3)

Chemical Structure

[0260] After dissolving 1.00 g of Compound 7 - 3 in 5.0 mL of dichloromethane, 1.89 mL of allyldiisopropylethylamine and 0.56 mL of methoxymethyl chloride were added, and the mixture was stirred at room temperature for 4 days. Water was added to the reaction solution, followed by liquid separation. After concentration to dryness, column purification was performed to obtain 0.96 g of Compound 7 - 4. (Compound 7 - 4)

Chemical Structure

[0261] After dissolving 0.96 g of Compound 7 - 4 in 10.0 mL of THF, 3.97 mL of a THF solution of tetrabutylammonium fluoride was added, and the mixture was stirred at room temperature overnight. An aqueous ammonium chloride solution and chloroform were added to the reaction solution, followed by liquid separation. After concentration to dryness, column purification was performed to obtain 0.57 g of Compound 7 - 5. (Compound 7 - 5)

Chemical formula

[0262] After dissolving 0.2 g of Compound 7 - 5 in 5.0 mL of THF, 0.191 g of phthalimide and 0.341 g of triphenylphosphine were added in sequence, and then 0.683 mL of diisopropyl azodicarboxylate was added. After stirring at room temperature overnight, water and diethyl ether were added to the reaction solution, followed by liquid separation. After concentration to dryness, column purification was performed to obtain 0.288 g of Compound 7 - 6. (Compound 7 - 6)

Chemical formula

[0263] After dissolving 0.288 g of Compound 7 - 6 in 5.0 mL of methanol, 0.292 mL of ethylenediamine was added, and the mixture was stirred at room temperature overnight. After adding water and chloroform to the reaction solution, the layers were separated, and by concentrating to dryness, 0.18 g of Compound 7 - 7 was obtained. (Compound 7 - 7)

Chemical Structure

[0264] CF3O-(CF2CF2O) n -(CF2O) m 1 g of the methyl ester represented by -CF2COOCH3 (n = 25, m = 25) and 79.7 mg of Compound 7 - 7 were dissolved in 1.5 mL of AK225, and the mixture was stirred at room temperature for 5 hours. After adding perfluorohexane and acetone to the reaction solution, the layers were separated, and by concentrating to dryness, 1.17 g of Compound 7 - 8 was obtained. (Compound 7 - 8)

Chemical Structure

[0265] After dissolving 0.99 g of Compound 7 - 8 in 1.5 mL of HFE7200, 44.2 μL of Karl Fischer catalyst and 7.2 μL of aniline were added. After stirring at room temperature for 30 minutes, 0.126 μL of trimethoxysilane was added and stirred at room temperature for 3 hours. After filtration and concentration to dryness, 0.96 g of Compound 7 - 9 was obtained. (Compound 7 - 9)

Chemical Structure

[0266] (Comparative Example 1) Compound C - 1 was obtained according to the method described in Example 1 of WO2017 / 212850 (n:m = 53:47, n + m = 43). (Compound C - 1)

Chemical Structure

[0267] <Formation of the surface treatment layer> The fluoropolyether group-containing silane compounds obtained in Examples 1 to 7 and Comparative Example 1 were diluted with Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 0.06% by mass to prepare a surface treatment agent. Thereafter, using a spray coater on a chemically strengthened glass (Gorilla 3 manufactured by Corning) whose surface was treated with atmospheric pressure plasma as a substrate, the surface treatment agent prepared above was applied. The coating amount was 60 g / m of the surface treatment agent 2 Then, the substrate coated with the surface treatment agent was heat-treated at 140°C for 30 minutes under atmospheric pressure to form a surface treatment layer.

[0268] <Method for measuring the static contact angle of water> The static contact angle was measured using a fully automatic contact angle meter DropMaster700 (manufactured by Kyowa Interface Science Co., Ltd.). Specifically, the substrate having the surface treatment layer to be measured was horizontally stationary, 2 μL of water was dropped onto the surface from a microsyringe, and the static contact angle was measured by photographing the still image 1 second after the drop with a video microscope. The static contact angle of water was measured at 5 different points on the surface treatment layer of the substrate, and the average value was used.

[0269] <Evaluation of eraser durability> (Initial evaluation) As the initial evaluation (0 eraser friction times), after wiping off the excess on the surface after the formation of the surface treatment layer, the static contact angle of water was measured. (Evaluation after the eraser durability test) For the formed surface treatment layer, using a rubbing tester (manufactured by Shin-Toyo Kagaku Co., Ltd.), the static contact angle of water was measured every 2500 reciprocations under the following conditions, and the measurement was carried out up to 10,000 times. The test environmental conditions were 25°C and 40%RH humidity. Eraser: Raber Eraser (manufactured by Minoan) Contact area: 6 mmφ Moving distance (one way): 40 mm Moving speed: 3,600 mm / min Load: 1 kg / 6 mmφ

[0270] The results are shown in Table 1.

[0271]

Table 1

[0272] (Synthesis Example 1) CF3O-(CF2CF2O) n -(CF2O) m -CF2COOH (n = 25, m = 25) 4.57 g of the carboxylic acid represented by was dissolved in 6.0 mL of metaxylene hexafluoride (mXHF), then 25 μl of DMF and 0.3 mL of thionyl chloride were added, stirred at room temperature, and then stirred at 90 °C for 3 hours. After 3 hours, the reaction solution was concentrated to dryness to obtain CF3O-(CF2CF2O) n -(CF2O) m -CF2COCl (n = 25, m = 25) the acid chloride represented by was obtained. The acid chloride synthesized above was dissolved in a mixed solvent of 6.0 mL of AK-225 and 1.0 mL of chloroform, then 0.205 g of hydrochloride of N,O-dimethylhydroxyamine was added. Subsequently, 0.323 mL of pyridine was added dropwise, and then stirred at 60 °C overnight. The reaction solution was washed with hydrochloric acid and then with water. Subsequently, washed with methanol and acetone, and concentrated to dryness to obtain 4.60 g of the following Compound 1A-1. (Compound 1A-1)

Chemical formula

[0273] After dissolving 5.10 g of Compound 1A-1 in 20.0 mL of HFE7200, the reaction solution was cooled to 0 °C. Subsequently, 2.46 mL of 1 mol / L diisobutylaluminum hydride (DIBAL-H) was added dropwise, and the mixture was stirred overnight. Subsequently, hydrochloric acid was added to the reaction solution and stirred, and then the hydrochloric acid phase was removed by liquid separation. Subsequently, it was washed with water and saturated brine, and dried over sodium sulfate. Subsequently, the solution was filtered and then concentrated to dryness. The composition obtained by concentration to dryness was washed with methanol and chloroform, and concentrated to dryness to obtain 5.1 g of Compound 1A-2. (Compound 1A-2)

Chemical Structure

[0274] After dissolving 5.1 g of Compound 1A-2 in 16.0 mL of HFE7200, 0.816 g of ethyl (triphenylphosphoranylidene) acetate was added at room temperature. Subsequently, 5 mL of THF and 10 mL of dichloromethane (DCM) were added, and the mixture was stirred overnight at room temperature. Perfluorohexane was added to the reaction solution, and it was washed in the order of methanol, acetone, and chloroform, and concentrated to dryness to obtain 5.2 g of Compound 1A-3. (Compound 1A-3)

Chemical Structure

[0275] 5.1 g of Compound 1A - 3 was dissolved in 16.0 mL of 2,2,3,3,3 - pentafluoro - 1 - propanol. Then, 1 g of palladium - on - activated carbon suspended in 5.0 mL of formic acid and 1.0 mL of water was added, and the mixture was stirred at room temperature overnight. After filtration through celite, it was concentrated to dryness. The resulting composition was dissolved in mXHF, and the solution obtained by passing through amino - silica gel was filtered and concentrated to dryness to obtain 4.59 g of Compound 1A - 4. (Compound 1A - 4)

Chemical Structure

[0276] 4.52 g of Compound 1A - 4 was dissolved in 10.0 mL of HFE7200. Then, 4.24 mL of allylmagnesium bromide (about 13% ethyl ether solution, about 0.7 mol / L) was added dropwise at 0 °C. After the addition, the mixture was stirred until the next morning. Hydrochloric acid was added to the reaction solution and stirred. The hydrochloric acid phase was removed by liquid separation and washed with water. Subsequently, it was washed with methanol, acetone, and chloroform in that order. After filtration, the solution was concentrated to dryness to obtain 4.60 g of Compound 1A - 5. (Compound 1A - 5)

Chemical Structure

[0277] After dissolving 0.8 g of Compound 1A - 5 in 1.5 mL of AK - 225, 0.149 mL of Hunig's base was added. Subsequently, 39.5 μl of methoxymethyl chloride was added, and the mixture was stirred at room temperature for 2 days and further at 35 °C for 3 days. Subsequently, the reaction solution was washed successively with methanol, acetone, and chloroform and concentrated to dryness to obtain 0.8 g of Compound 1A - 6. (Compound 1A - 6)

Chemical formula

[0278] (Synthesis Example 2) 1.27 g of Compound 3-3 was dissolved in a mixed solvent of 3.0 mL of AK-225 and 0.7 mL of DMF, and then 67.0 mg of imidazole was added. Subsequently, 64.0 μL of trimethylsilyl chloride was added, and the mixture was stirred overnight at room temperature. Subsequently, after washing with saturated aqueous sodium hydrogen carbonate solution, water, and methanol, and concentrating to dryness, 0.71 g of Compound 2A-1 was obtained. (Compound 2A-1)

Chemical Structure

[0279] (Synthesis Example 3) CF3O-(CF2CF2O) n -(CF2O) m 1.71 g of the alcohol represented by -CF2CH2OH (n = 25, m = 25) was dissolved in a mixed solvent of 3.0 mL of AK-225 and 0.4 mL of DMF, and then 23 mg of sodium hydride was added, and the mixture was stirred at room temperature for 30 minutes. Subsequently, 0.112 mL of methyl chloroacetate and 15.7 mg of tetrabutylammonium iodide (TBAI) were added, and the mixture was stirred overnight at 80°C. Hydrochloric acid was added to the reaction solution and stirred, and then the hydrochloric acid layer was removed by liquid separation and washed with water and acetone. After concentration to dryness, it was purified by silica gel column chromatography to obtain 0.93 g of Compound 3A-1. (Compound 3A-1)

Chemical Structure

[0280] After dissolving 1.34 g of Compound 3A-1 in 4.0 mL of HFE7200, the solution was cooled to 0 °C, and 1.44 mL of allylmagnesium bromide (about 13% ethyl ether solution, about 0.7 mol / L) was added dropwise. After the addition, the mixture was stirred until the next morning. Subsequently, hydrochloric acid was added to the reaction solution and stirred, and then the hydrochloric acid layer was removed by liquid separation and washed with water and acetone. After concentration to dryness, 1.36 g of Compound 3A-2 was obtained. (Compound 3A-2)

Chemical formula

[0281] After dissolving 0.56 g of Compound 3A-2 in 1.3 mL of AK-225, 74.0 μl of Hunig's base was added. Subsequently, 22.0 μl of methoxymethyl chloride was added, and the mixture was stirred at 37 °C overnight. Subsequently, 74.0 μl of Hunig's base and 23.0 μl of methoxymethyl chloride were added, and the mixture was stirred for 5 days. The reaction solution was washed with methanol, acetone, and chloroform. After concentrating this solution to dryness and purifying it by silica gel column, 0.597 g of Compound 3A-3 was obtained. (Compound 3A-3)

Chemical formula

[0282] (Synthesis Example 4) CF3O-(CF2CF2O) n -(CF2O) m 4.0 g of the terminal allyl compound represented by -CF2CH2CH=CH2 (n = 22, m = 22), 0.43 g of methyl p-bromobenzoate, 22.5 mg of Pd(OAc)2, 52.4 mg of triphenylphosphine, 6.0 mL of mXHF, 1.0 mL of DMF, and 0.307 mL of triethylamine were added at room temperature and stirred at 100 °C overnight. Subsequently, it was washed with methanol, acetone, and chloroform, concentrated to dryness, and then purified by silica gel column to obtain 1.63 g of Compound 4A-1. (Compound 4A-1) [Chemical formula] 1 1H NMR (mXHF, 400 MHz) δ: 3.25 - 3.40 (m, 2 H), 4.18 (s, 3 H), 6.50 - 6.63 (m, 1 H), 6.80 - 6.96 (m, 1 H).

[0283] 1.61 g of Compound 4A-1 was dissolved in 15.0 mL of 2,2,3,3,3-pentafluoro-1-propanol, and then a suspension of 0.6 g of palladium on activated carbon in 5.0 mL of formic acid and 1.0 mL of water was added and stirred at room temperature overnight. Subsequently, it was filtered through celite, concentrated to dryness, and then purified by silica gel column to obtain 0.9 g of Compound 4A-2. (Compound 4A-2) [Chemical formula] 11H NMR (mXHF, 400 MHz) δ: 2.15 - 2.30 (m, 2 H), 2.30 - 2.50 (m, 2 H), 3.00 - 3.10 (m, 2 H), 4.20 (s, 3 H); 19 19F NMR (mXHF, 400 MHz) δ: -54.0, -55.8, -56.5, -57.5, -58.0, -58.3, -60.0, -72.4, -74.0, -88.7, -91.0, -93.0.

[0284] After dissolving 0.94 g of Compound 4A-2 in 5.0 mL of HFE7200, the solution was cooled to 0 °C, and 1.0 mL of allylmagnesium bromide (approx. 13% ethyl ether solution, approx. 0.7 mol / L) was added dropwise. After the addition, the mixture was stirred until the next morning. Subsequently, hydrochloric acid was added to the reaction solution and stirred, and then the hydrochloric acid layer was removed by liquid separation. The residue was washed with water, methanol, and acetone, concentrated to dryness, and purified by silica gel column chromatography to obtain 0.551 g of Compound 4A-3. (Compound 4A-3)

Chemical Structure

[0285] After dissolving 0.53 g of Compound 4A-3 in 3.0 mL of AK-225, 0.135 mL of Hunig's base was added. Subsequently, 39.9 μL of methoxymethyl chloride was added, and the mixture was stirred at 37 °C for 4 days. The reaction solution was washed with methanol and chloroform, concentrated to dryness, and purified by silica gel column chromatography to obtain 0.55 g of Compound 4A-4. (Compound 4A-4)

Chemical formula

[0286] (Synthesis Example 5) CF3O-(CF2CF2O) n -(CF2O) m After dissolving 6.2 g of the terminal allyl compound represented by -CF2CH2CH=CH2 (n = 22, m = 22) in 12 mL of AK-225, 2.18 mL of methyl hexenoate and 65.8 mg of Grubbs catalyst (second generation) were added. After stirring overnight at room temperature, the mixture was washed with methanol and acetone, concentrated to dryness, and purified by silica gel column chromatography to obtain 2.64 g of Compound 5A-1. (Compound 5A-1)

Chemical formula

[0287] After dissolving 2.63 g of Compound 5A-1 in 10.0 mL of 2,2,3,3,3-pentafluoro-1-propanol, 0.48 g of palladium on activated carbon was added. Subsequently, the mixture was stirred overnight at room temperature under a hydrogen gas atmosphere, filtered, concentrated to dryness, and 2.58 g of Compound 5A-2 was obtained. (Compound 5A-2)

Chem.

[0288] After dissolving 2.57 g of Compound 5A-2 in 5.0 mL of HFE7200, the solution was cooled to 0 °C, and 2.75 mL of allylmagnesium bromide (about 13% ethyl ether solution, about 0.7 mol / L) was added dropwise. After the addition, the mixture was stirred until the next morning. Hydrochloric acid was added to the reaction solution and stirred, and then the hydrochloric acid phase was removed by liquid separation. The residue was washed with water, methanol, and acetone. After concentration to dryness and purification by silica gel column chromatography, 1.99 g of Compound 5A-3 was obtained. (Compound 5A-3)

Chem.

Industrial Applicability

[0289] The fluoropolyether group-containing silane compound of the present disclosure can be suitably used to form a surface treatment layer on the surfaces of various substrates, particularly optical members that require tribological durability.

Claims

1. A fluoropolyether group-containing compound represented by formula (a27) or formula (a28): 【Chemical 1】 [In the formula: is a group represented by; R Ｆ１ is represented by Rf １ -R Ｆ -O ｑ -; R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ represented by -; Rf １ is an optionally substituted C １－１６ alkyl group; Rf ２ is an optionally substituted C １－６ alkylene group having one or more fluorine atoms; R Ｆ is, in each occurrence, independently of one another, of 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 - a, b, c, d, e, and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more. The order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f attached is arbitrary in the formula; p is 0 or 1; R Ｆａ is, in each occurrence, independently, a hydrogen atom, a fluorine atom or a chlorine atom; q is independently 0 or 1; is represented by; -X ６ - is, in each occurrence, independently of one another, -X ６１ -CR ６１ =CR ６２ -X ６２ -, or -X ６３ - is represented by; X ６１ are each independently -(CR ６０ ２ ) ｎ６１１ -((CH ２ ) ｎ６１４ -Y ６１ -(CH ２ ) ｎ６１３ ) ｎ６１２ - n613 are each independently 0 or 1; R ６０ represents, in each occurrence, independently of one another, a hydrogen atom, a halogen atom, or a monovalent organic group; Y ６１ is, independently at each occurrence, O, CONR １５ , NR １５ , S, or an arylene group; n614 are each independently 0 or 1; n611 is an integer from 0 to 10; n612 is an integer from 0 to 10; The order of existence of each repeating unit enclosed in parentheses with n611 or n612 attached is arbitrary in the formula; n611' is an integer from 0 to 10; X ６２ is, independently of each other, -(CR ６０ ２ ) ｎ６１１’ -((CH ２ ) ｎ６１４ -Y ６１ -(CH ２ ) ｎ６１３ ) ｎ６１２’ - represented by; n612' is an integer from 0 to 10; The order of existence of each repeating unit enclosed in parentheses with n611' or n612' attached is arbitrary in the formula; is represented by; R １５ is, in each occurrence independently, a hydrogen atom, a group having an aromatic ring, a C １－６ alkyl group, —O—C １－６ alkyl group, or a C ３－１０ cycloalkyl group; R ６１ and R ６２ are each independently a hydrogen atom or a monovalent organic group; X ６３ is -(CR ６０ ２ ) ｎ６２１ -((CH ２ ) ｎ６１４ -Y ６１ -(CH ２ ) ｎ６１３ ) ｎ６２２ - n621 is an integer from 0 to 10; n622 is an integer from 0 to 10; The order of existence of each repeating unit enclosed in parentheses with n621 or n622 attached is arbitrary in the formula, and the sum of n621 and n622 is 1 or more;

2. R ６５ is each independently a hydrogen atom or a monovalent organic group; Z ２３ each independently represents a single bond or a divalent organic group.] A method for producing a fluoropolyether group-containing compound, comprising the step of obtaining a compound represented by formula (a23) or formula (a24): [In the formula: [Chemical 2] The compound represented by and Hal-J-Z ２３ -CH=CH ２ are reacted to obtain formula (a25) or formula (a26): [Chemical Formula 3] is a group represented by; a, b, c, d, e, and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more. The order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f attached is arbitrary in the formula; p is 0 or 1; R Ｆ１ is represented by Rf １ -R Ｆ -O ｑ -; R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ and is represented by -; Rf １ is an optionally substituted C １－１６ alkyl group with one or more fluorine atoms; Rf ２ is an alkylene group which may be substituted by one or more fluorine atoms; １－６ ​ R Ｆ is, in each occurrence independently, of 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 - q is independently 0 or 1; is represented by; R Ｆａ is, in each occurrence, independently a hydrogen atom, a fluorine atom or a chlorine atom; is represented by; n613 are each independently 0 or 1; -X ６ -, in each occurrence, is independently -X ６１ -CR ６１ =CR ６２ -X ６２ -, or -X ６３ - n614 are each independently 0 or 1; X ６１ are each independently -(CR ６０ ２ ) ｎ６１１ -((CH ２ ) ｎ６１４ -Y ６１ -(CH ２ ) ｎ６１３ ) ｎ６１２ - n611 is an integer from 0 to 10; R ６０ each occurrence independently represents a hydrogen atom, a halogen atom, or a monovalent organic group; Y ６１ is, in each occurrence independently, O, CONR １５ , NR １５ , S, or an arylene group; n612 is an integer from 0 to 10; The order of existence of each repeating unit enclosed in parentheses with n611 or n612 attached is arbitrary in the formula; n611' is an integer from 0 to 10; n612' is an integer from 0 to 10; The order of existence of each repeating unit enclosed in parentheses with n611' or n612' attached is arbitrary in the formula; X ６２ is, independently of each other, -(CR ６０ ２ ) ｎ６１１’ -((CH ２ ) ｎ６１４ -Y ６１ -(CH ２ ) ｎ６１３ ) ｎ６１２’ -represented by; is represented by; n621 is an integer from 0 to 10; n622 is an integer from 0 to 10; R １５ is, in each occurrence independently, a hydrogen atom, a group having an aromatic ring, a C １－６ alkyl group, -O-C １－６ alkyl group, or a C ３－１０ cycloalkyl group; R ６１ and R ６２ are each independently a hydrogen atom or a monovalent organic group; X ６３ are each independently -(CR ６０ ２ ) ｎ６２１ -((CH ２ ) ｎ６１４ -Y ６１ -(CH ２ ) ｎ６１３ ) ｎ６２２ - The order of existence of each repeating unit enclosed in parentheses with n621 or n622 attached is arbitrary in the formula, and the sum of n621 and n622 is 1 or more; The order of existence of each repeating unit enclosed in parentheses with n621 or n622 attached is arbitrary in the formula, and the sum of n621 and n622 is 1 or more; n622 is an integer from 0 to 10; The order of presence of each repeating unit enclosed in parentheses with n621 or n622 is arbitrary in the formula, and the sum of n621 and n622 is 1 or more; R ６３ is, in each occurrence, independently a hydrogen atom or a monovalent organic group; Hal represents a halogen atom; J represents Mg, Cu, Pd or Zn; Z ２３ each independently represents a single bond or a divalent organic group.]]

3. Rf1 is a C1-16 perfluoroalkyl group; Rf2 is a C1-6 perfluoroalkylene group. The fluoropolyether group-containing compound according to claim 1.

4. RF is of formula (f1), (f2), (f3), (f4) or (f5): -(OC3F6)d-(OC2F4)e - (f1) [In the formula, d is an integer from 1 to 200, and e is 0 or 1. ] -(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f - (f2) [In the formula, c and d are each independently an integer of 0 or more and 30 or less, e and f are each independently 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 presence of each repeating unit enclosed in parentheses with the subscript c, d, e or f is arbitrary in the formula. ] -(R6-R7)g - (f3) [In the formula, R6 is OCF2 or OC2F4, R7 is a group selected from OC2F4, OC3F6, OC4F8, OC5F10 and OC6F12, or a combination of 2 or 3 groups independently selected from these groups, g is an integer from 2 to 100. ] -(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f - (f4) [In the formula, e is an integer from 1 to 200, and a, b, c, d and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1, and the order of presence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula. ] -(OC₆F₁₂)ₐ-(OC₅F₁₀)ᵦ-(OC₄F₈)ᶜ-(OC₃F₆)ᵈ-(OC₂F₄)ᵉ-(OCF₂)ᶠ-(f5) [In the formula, f is an integer of 1 or more and 200 or less, and a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e, and f is at least 1. Also, the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] The fluoropolyether group-containing compound according to claim 1 or 3, which is a group represented by the formula.

5. The fluoropolyether group-containing compound according to claim 1 or 3, wherein q is 0.

6. R₆₅ is a hydrogen atom, a benzyl group, a methoxyphenyl group, a benzoyl group, a trityl group, -SiR₇₁₃, or -(R₇₂-O)ₙ₇-R₇₃, R₇₁ is each independently a C₁₋₄ alkyl group, R₇₂ is each independently a C₁₋₄ alkylene group, n₇ is each independently an integer of 1 to 10; R₇₃ is each independently a hydrogen atom or a monovalent hydrocarbon group which may contain a ring structure, The fluoropolyether group-containing compound according to claim 1 or 3.

7. X₆ is each independently represented by -X₆₃-, X₆₃ is represented by -(CR₆₀₂)ₙ₆₂₁-((CH₂)ₙ₆₁₄-Y₆₁-(CH₂)ₙ₆₁₃)ₙ₆₂₂-, R₆₀ is each independently a hydrogen atom or a halogen atom at each occurrence; Y₆₁ is each independently O, CONR₁₅, NR₁₅, S, or an arylene group at each occurrence; R₁₅ is each independently a hydrogen atom, a group having an aromatic ring, a C₁₋₆ alkyl group, -O-C₁₋₆ alkyl group, or a C₃₋₁₀ cycloalkyl group at each occurrence; n₆₂₁ is an integer of 0 to 10; n₆₂₂ is an integer of 0 to 10; The order of existence of each repeating unit enclosed in parentheses with n₆₂₁ or n₆₂₂ is arbitrary in the formula, and the sum of n₆₂₁ and n₆₂₂ is 1 or more, n₆₁₃ is each independently 0 or 1; n614 is, independently of each other, 0 or 1, The fluoropolyether group-containing compound according to claim 1 or 3.

8. Rf1 is a C1-16 perfluoroalkyl group; Rf2 is a C1-6 perfluoroalkylene group, The method for producing a fluoropolyether group-containing compound according to claim 2.

9. RF is of formula (f1), (f2), (f3), (f4) or (f5): -(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) [wherein, c and d are each independently an integer of 0 or more and 30 or less, e and f are each independently 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 existence of each repeating unit enclosed in parentheses with a subscript c, d, e or f is arbitrary in the formula. ] -(R6-R7)g - (f3) [wherein, R6 is OCF2 or OC2F4, R7 is a group selected from OC2F4, OC3F6, OC4F8, OC5F10 and OC6F12, or a combination of 2 or 3 groups independently selected from these groups, g is an integer of 2 to 100. ] -(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f - (f4) [wherein, 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 sum of a, b, c, d, e and f is at least 1, and the order of existence of each repeating unit enclosed in parentheses with a subscript a, b, c, d, e or f is arbitrary in the formula. ] [In the formula, f is an integer of 1 or more and 200 or less, and a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e, and f is at least 1. Also, the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f attached is arbitrary in the formula.] The method for producing a fluoropolyether group-containing compound according to claim 2 or 8, which is a group represented by the formula:

10. The method for producing a fluoropolyether group-containing compound according to claim 2 or 8, wherein q is 0.

11. X6 is each independently represented by -X63-, X63 is represented by -(CR602)n621-((CH2)n614-Y61-(CH2)n613)n622-, R60 is each independently a hydrogen atom or a halogen atom at each occurrence; Y61 is each independently O, CONR15, NR15, S, or an arylene group at each occurrence; R15 is each independently a hydrogen atom, a group having an aromatic ring, a C1-6 alkyl group, -O-C1-6 alkyl group, or a C3-10 cycloalkyl group at each occurrence; n621 is an integer of 0 to 10; n622 is an integer of 0 to 10; The order of existence of each repeating unit enclosed in parentheses with n621 or n622 attached is arbitrary in the formula, and the sum of n621 and n622 is 1 or more. n613 is each independently 0 or 1; n614 is each independently 0 or 1, The method for producing a fluoropolyether group-containing compound according to claim 2 or 8.

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