Fluorine-atom-containing silane compound

Abstract

To provide a fluorine-atom-containing silane compound that achieves further enhancement in abrasion durability and weather resistance.SOLUTION: The fluorine-atom-containing silane compound is represented by formula (A1) or formula (A2), wherein each symbol has the same meaning as described in the specification.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a fluorine atom-containing silane compound, a composition containing the fluorine atom-containing silane compound, and a method for producing the same. [Background technology]

[0002] It is known that a silane compound having a fluorine atom in the molecule (hereinafter, sometimes referred to as a "fluorine atom-containing silane compound") can contribute to the formation of a layer (hereinafter, sometimes referred to as a "surface treatment layer") having physical properties such as water repellency and oil repellency (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-80448 Summary of the Invention [Problem to be solved by the invention]

[0004] Attempts have been made to further improve friction durability compared to conventional techniques. An object of the present disclosure is to provide a fluorine atom-containing silane compound that has improved friction durability and weather resistance. [Means for solving the problem]

[0005] The present disclosure provides the following [1] to [9]. [1] Formula (A1) or (A2): [ka] [In formula: R F1 is Rf 1 -R F -O q - and; R F2 is -Rf 2p -R F -O q - and; Rf 1 C optionally substituted with one or more fluorine atoms 1-16 is an alkyl group; Rf 2 C optionally substituted with one or more fluorine atoms 1-6 is an alkylene group; R F are each independently a divalent fluorine atom-containing group; p is 0 or 1; Each q is independently 0 or 1; R Si are each independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a silicon atom to which a monovalent organic group is bonded; and At least one R Si contains a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto. Fluorine atom-containing silane compound represented by the formula: [2] R F are each independently represented by the following formula (f1) or formula (f2): -(OC j R e 2j ) j1 -(OC h R e 2h-2 ) h1 - (f1) [In formula: -OC j R e 2j - are each independently a repeating unit having a linear or branched chain; -OC h R e 2h-2 - are each independently a repeating unit having a ring structure; R e are each independently a hydrogen atom, a fluorine atom, or a chlorine atom; However, R F At least one R eis a fluorine atom; j's are each independently an integer from 1 to 6; h is independently an integer from 1 to 7; j1 is an integer greater than or equal to 0; h1 is an integer greater than or equal to 0; The sum of j1 and h1 is greater than or equal to 1; The repeating units enclosed in parentheses with j1 or h1 may be present in any order in the formula. -(C s R e1 2s ) s1 -(R d ) s2 - (f2) [In formula: Each s is independently an integer from 1 to 10; R e1 are each independently a hydrogen atom, a fluorine atom, or a chlorine atom; R d each independently represents an arylene group optionally substituted with a fluorine atom; However, R d or R e1 at least one of which is a fluorine atom; s1 is an integer greater than or equal to 0; s2 is an integer greater than or equal to 0; The sum of s1 and s2 is greater than or equal to 1; The repeating units enclosed in parentheses with s1 or s2 may occur in any order in the formula.] The fluorine atom-containing silane compound according to [1], wherein the fluorine atom-containing silane compound is a group represented by the formula: [3] R F are each independently of the formula: -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3R Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 - [In formula: a1, b1, c1, d1, e1, and f1 each independently represent an integer of 0 to 200, and the sum of a1, b1, c1, d1, e1, and f1 is 1 or more; The order of occurrence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula; R Fa is independently in each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom. The fluorine atom-containing silane compound according to [1] or [2], wherein the fluorine atom-containing silane compound is a group represented by the formula: [4] R F are each independently represented by the following formula (f11), (f12), (f13), (f14), (f15) or (f16): -(OC3F6) d1 -(OC2F4) e1 - (f11) [In formula: d1 is an integer from 1 to 200; e1 is 0 or 1.]; -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 - (f12) [In formula: c1 and d1 each independently represent an integer of 0 to 30; e1 and f1 each independently represent an integer of 1 or more and 200 or less; The sum of c1, d1, e1 and f1 is greater than or equal to 2; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c1, d1, e1, or f1 in the formula is arbitrary.]; -(R 71 -R 72 ) g1 -R 73 - (f13) [In formula: R 71 is OCF2 or OC2F4; R 72are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups; R 73 is a single bond or OCF2, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups selected from these groups; g1 is an integer from 2 to 100. -(R 71 -R 72 ) g1 -R r -(R 72’ -R 71’ ) g1’ - (f14) [In formula: R 71 is OCF2 or OC2F4; R 72 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups; R 71’ is OCF2 or OC2F4; R 72’ are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups; g1 is an integer from 2 to 100; g1' is an integer from 2 to 100; R r is the following group: [ka] (In the formula, * indicates the bonding position.) ]; -(OC6F12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 - (f15) [In formula: e1 is an integer of 1 or more and 200 or less, a1, b1, c1, d1, and f1 are each independently an integer of 0 or more and 200 or less, the sum of a1, b1, c1, d1, e1, and f1 is at least 1, and the order of the repeating units enclosed in parentheses with a1, b1, c1, d1, e1, or f1 in the formula is arbitrary.] -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 - (f16) [In formula: f1 is an integer of 1 or more and 200 or less, a1, b1, c1, d1, and e1 are each independently an integer of 0 or more and 200 or less, the sum of a1, b1, c1, d1, e1, and f1 is at least 1, and the order of the repeating units enclosed in parentheses with a1, b1, c1, d1, e1, or f1 in the formula is arbitrary.] The fluorine atom-containing silane compound according to any one of [1] to [3], wherein the fluorine atom is a group represented by the formula: [5] R Si is expressed as equation (S1): [ka] [In formula: R a1 are each independently -Z 1 -SiR 41 r1 R 42 r2 R 43 r3 and; Z 1 are each independently an oxygen atom or a divalent organic group; R 41 are each independently -Z 1’ -SiR 41’ r1’ R 42’ r2’ R 43’ r3’ and; Z 1’ are each independently an oxygen atom or a divalent organic group; R 41’ are each independently -Z 1” -SiR 41” r1” R 42” r2” and; Z 1” are each independently an oxygen atom or a divalent organic group; R 41” are each independently a hydroxyl group or a hydrolyzable group; R 42” are each independently a hydrogen atom or a monovalent organic group; Each r1" is independently an integer of 0 to 3; r2″ are each independently an integer of 0 to 3; R 42’ are each independently a hydroxyl group or a hydrolyzable group; R 43’ are each independently a hydrogen atom or a monovalent organic group; Each r1' is independently an integer of 0 to 3; Each r2' is independently an integer of 0 to 3; Each r3' is independently an integer of 0 to 3; R 42 are each independently a hydroxyl group or a hydrolyzable group; R 43 are each independently a hydrogen atom or a monovalent organic group; Each r1 is independently an integer of 0 to 3; Each r2 is independently an integer of 0 to 3; Each r3 is independently an integer of 0 to 3; R b1 are each independently a hydroxyl group or a hydrolyzable group; R c1 are each independently a hydrogen atom or a monovalent organic group; Each k1 independently represents an integer of 0 to 3; Each l1 is independently an integer of 0 to 3; Each m1 independently represents an integer of 0 to 3; However, in formula (S1), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group.] The fluorine atom-containing silane compound according to any one of [1] to [4], represented by the following formula: [6] Z 1 are each independently 1-6 Alkylene group, -(CH2) z1 -O-(CH2) z2 -or-(CH2) z3 -phenylene-(CH2) z4 - and; The fluorine atom-containing silane compound according to [5], wherein z1 to z4 are each independently an integer of 0 to 6. [7] A composition comprising the fluorine atom-containing silane compound according to any one of [1] to [6]. [8] An article having a substrate and a layer formed on the surface of the substrate from the composition according to [7]. [9] Formula (B31) or Formula (B41): [ka] By adding a methylenylating reagent to a compound represented by formula (B1) or formula (B2): [ka] forming a compound represented by A method for producing a compound comprising: [In formula: R F1 is Rf 1 -R F -O q - and; R F2 is -Rf 2 p -R F -O q - and; Rf 1 C optionally substituted with one or more fluorine atoms 1-16 is an alkyl group; Rf 2 C optionally substituted with one or more fluorine atoms 1-6 is an alkylene group; R F are each independently a divalent fluorine atom-containing group; p is 0 or 1; Each q is independently 0 or 1. [Effects of the Invention]

[0006] According to the present disclosure, it is possible to provide a fluorine atom-containing silane compound that has improved abrasion resistance durability and weather resistance. DETAILED DESCRIPTION OF THE INVENTION

[0007] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, resulting from the elimination of one hydrogen atom from a hydrocarbon. Examples of such hydrocarbon groups include, but are not limited to, 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 "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. The 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.

[0008] As used herein, the substituent of the "hydrocarbon group" is not particularly limited, but examples thereof include a halogen atom; a C 1-6 Alkyl group, C 2-6 Alkenyl group, C 2-6 Alkynyl group, C 3-10 Cycloalkyl groups, C 3-10 Unsaturated cycloalkyl groups, 5-10 membered heterocyclyl groups, 5-10 membered unsaturated heterocyclyl groups, C 6-10 Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0009] As used herein, the term "organic group" refers to a group containing a carbon atom. For example, a divalent organic group refers to a divalent group containing carbon. The divalent organic group is not particularly limited, but examples thereof include divalent groups in which 1 to 9 hydrogen atoms have been eliminated from a hydrocarbon group. The divalent organic group is not particularly limited, but examples thereof include divalent groups in which one hydrogen atom has been eliminated from a hydrocarbon group.

[0010] 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 h1 , -OCOR h1 , -ON=CR h1 2, -NR h1 2, -NHR h1 , halogen (wherein R h1 represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), and preferably -OR h1 (i.e., an alkoxy group). h1 Examples of the alkyl group include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, with methyl and ethyl groups being more preferred.

[0011] (Fluorine atom-containing silane compound) The fluorine atom-containing silane compound is represented by the formula (A1) or (A2): [ka] It is expressed as:

[0012] R F1 is Rf 1 -R F -O q -It is.

[0013] R F2 is -Rf 2 p -R F -O q -It is.

[0014] p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0015] Each q is independently 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.

[0016] Rf 1 C optionally substituted with one or more fluorine atoms 1-16 It is an 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 straight or branched C 1-3 alkyl group, more preferably a straight-chain C 1-6 Alkyl groups, especially straight-chain C 1-3 It is an alkyl group.

[0017] Above Rf 1 is preferably C substituted by one or more fluorine atoms 1-16 alkyl group, more preferably C 1-16 It is a perfluoroalkyl group. 1-16The perfluoroalkyl group may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-6 Perfluoroalkyl groups, especially straight-chain or branched C 1-3 A perfluoroalkyl group, more preferably a linear C 1-6 Perfluoroalkyl groups, especially linear C 1-3 It is a perfluoroalkyl group.

[0018] In one embodiment, Rf 1 C optionally substituted with one or more fluorine atoms 1-6 It is an alkyl group. 1-6 The "alkyl group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-3 It is an alkyl group.

[0019] In one embodiment, the above C 1-6 The alkyl group is a straight-chain C 1-6 alkyl group, preferably C 1-3 Rf is an alkyl group. 1 In one embodiment, is CF3-; in another embodiment, is CF3CF2-; and in yet another embodiment, is CF3CF2CF2-.

[0020] In the above embodiment, Rf 1 is preferably C substituted by one or more fluorine atoms 1-6 alkyl group, more preferably C 1-6 In this embodiment, the C 1-6 The perfluoroalkyl group may be linear or branched, and is preferably a linear C 1-6 Perfluoroalkyl groups, especially linear C 1-3 It is a perfluoroalkyl group.

[0021] Rf 2 C optionally substituted with one or more fluorine atoms 1-6 It is an alkylene group. 1-6The alkylene group may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-3 It is preferably a linear alkylene group. 1-3 It is an alkylene group.

[0022] Above Rf 2 is preferably C substituted by one or more fluorine atoms 1-6 is an alkylene group, more preferably C 1-6 A perfluoroalkylene group, more preferably C 1-3 It is a perfluoroalkylene group.

[0023] Above C 1-6 The perfluoroalkylene group may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-3 A perfluoroalkylene group, more preferably a linear C 1-3 A perfluoroalkylene group, specifically, -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0024] R F are each independently a divalent fluoropolyether group (PFPE group). The divalent fluorine atom-containing group refers to a divalent organic group in which at least a portion of the hydrogen atoms are substituted with fluorine atoms.

[0025] Preferably, R F are each independently a group R represented by the following formula (f1): F11 Or a group R represented by the following formula (f2): F12 It is expressed as: -(OC j R e 2j ) j1 -(OC h R e 2h-2 ) h1 - (f1) -(C s R e1 2s ) s1 -(R d )s2 - (f2) In this specification, the left side of formulas (f1) and (f2) is Rf 1 -or-Rf 2 p -, and the right side is -O q -, respectively.

[0026] ·R F11 -(OC j R e 2j ) j1 -(OC h R e 2h-2 ) h1 - (f1)

[0027] -OC j R e 2j Each - is independently a repeating unit having a straight chain or a branched chain. -OC h R e 2h-2 Each - is independently a repeating unit having a ring structure.

[0028] R e are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, provided that R F11 In this case, at least one R e is a fluorine atom.

[0029] R e is preferably a fluorine atom.

[0030] Each j is independently an integer of 1 to 6.

[0031] Each h is independently an integer of 1 to 7.

[0032] j1 is an integer equal to or greater than 0. h1 is an integer equal to or greater than 0. However, the sum of j1 and h1 is at least 1, and preferably at least 2. The order of the repeating units enclosed in parentheses with j1 or h1 is arbitrary in the formula.

[0033] In one embodiment, -(OC j R e 2j ) j1 -teeth, -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3R Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 - It is expressed as: a1, b1, c1, d1, e1, and f1 each independently represent an integer of 0 to 200, the sum of a1, b1, c1, d1, e1, and f1 is 1 or more, and the order of the repeating units enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula. By having such groups, a surface treatment layer having water repellency, oil repellency, chemical resistance, abrasion resistance, weather resistance (for example, ultraviolet (UV) resistance), etc. can be formed.

[0034] R Fa are each independently a hydrogen atom, a chlorine atom, or a fluorine atom.

[0035] Above R Fa is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom.

[0036] Preferably, a1, b1, c1, d1, e1 and f1 may each independently be an integer of 0 to 100.

[0037] The sum of a1, b1, c1, d1, e1, and f1 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 a1, b1, c1, d1, e1, and f1 is preferably 200 or less, more preferably 100 or less, even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0038] (OC j R e 2j ) can include, for example, the following repeating units: -(OCF 12 )- may be -(OCF2CF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. 10 )- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)- (i.e., in the above formula, R Fa is a fluorine atom) may be any of -(OCFCFCF)-, -(OCF(CF)CF)-, and -(OCFCF(CF))-. -(OCF)- may be any of -(OCFCF)- and -(OCF(CF))-.

[0039] In one embodiment, the repeating unit is linear.

[0040] In one embodiment, the repeating unit is branched.

[0041] In one embodiment, (OC j R e 2j )teeth, -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3R Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 - Each symbol is as described above.

[0042] -(OC h R e 2h-2 )-C h R e 2h-2 can be a three-, four-, five-, or six-membered ring as shown below. [ka] [In the formula, * indicates the bonding position.]

[0043] In one embodiment, R F11 is independently in each occurrence a group represented by any one of the following formulas (f11) to (f16). -(OC3F6) d1 -(OC2F4) e1 - (f11) [wherein d1 is an integer of 1 to 200; and e1 is 0 or 1, preferably 1.] -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 - (f12) [In the formula, c1 and d1 each independently represent an integer of 0 or more and 30 or less, and e1 and f1 each independently represent an integer of 1 or more and 200 or less; The sum of c1, d1, e1 and f1 is greater than or equal to 2; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c1, d1, e1, or f1 in the formula is arbitrary.]; -(R 71 -R 72 ) g1 -R 73 - (f13) [In the formula, R 71 is OCF2 or OC2F4; R 72 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups; R 73 is a single bond or OCF2, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups selected from these groups; g1 is an integer from 2 to 100. -(R 71 -R 72 ) g1 -R r -(R 72’ -R 71’ ) g1’ - (f14) [In the formula, R 71 is OCF2 or OC2F4; R 72 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups; R 71’ is OCF2 or OC2F4; R 72’ are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12or a combination of two or three groups independently selected from these groups; g1 is an integer from 2 to 100; g1' is an integer from 2 to 100; R r teeth, [ka] (In the formula, * indicates the bonding position.) ]; -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 - (f15) [In the formula, e1 is an integer of 1 or more and 200 or less, a1, b1, c1, d1, and f1 are each independently an integer of 0 or more and 200 or less, the sum of a1, b1, c1, d1, e1, and f1 is at least 1, and the order of the repeating units enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula.] -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 - (f16) [In the formula, f1 is an integer of 1 or more and 200 or less, a1, b1, c1, d1, and e1 are each independently an integer of 0 or more and 200 or less, the sum of a1, b1, c1, d1, e1, and f1 is at least 1, and the order of the repeating units enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula.]

[0044] In the above formula (f11), d1 is preferably an integer of 5 to 200, more preferably 10 to 100, even more preferably 15 to 50, for example, an integer of 25 to 35. In the above formula (f11), (OC3F6) is preferably a group represented by (OCF2CF2CF2) or (OCF(CF3)CF2), more preferably a group represented by (OCF2CF2CF2). In the above formula (f11), (OC2F4) is preferably a group represented by (OCF2CF2) or (OCF(CF3)), more preferably a group represented by (OCF2CF2).

[0045] In the formula (f12), e1 and f1 are each independently an integer of preferably 5 or more and 200 or less, more preferably 10 to 200. The sum of c1, d1, e1 and f1 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 formula (f12) is preferably -(OCF2CF2CF2CF2) c1 -(OCF2CF2CF2) d1 -(OCF2CF2) e1 -(OCF2) f1 In another embodiment, formula (f12) is a group represented by -(OC2F4) e1 -(OCF2) f1 It may also be a group represented by the formula -.

[0046] In the above formula (f13), R 71 is preferably OC2F4. In the above (f13), R 72is 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 (f13), g1 is preferably an integer of 3 or more, more preferably 5 or more. The above g1 is preferably an integer of 50 or less. In the above formula (f13), 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 (f13) is preferably -(OC2F4-OC3F6) g1 -or-(OC2F4-OC4F8) g1 In one embodiment, R 73 is a single bond. 73 are OCF2, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups selected from these groups. 73 is preferably a group selected from OCF2, OC2F4, OC3F6, and OC4F8, or a combination of two or three groups selected from these groups, and more preferably -OC2F4OC3F6-.

[0047] In the above formula (f14), R 71 , R 72 and g1 have the same meanings as those in the formula (f13) above, and have the same embodiments. 71’ , R 72’ and g1′ are R 71 , R 72 and g1 and have the same meaning and aspects. r is preferably [ka] [In the formula, * indicates the bonding position.] and more preferably [ka] [In the formula, * indicates the bonding position.] is.

[0048] In the above formula (f15), e1 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 a1, b1, c1, d1, e1, and f1 is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0049] In the above formula (f15), R F11 The repeating unit at the terminal portion may be -(OCF2CF2OCF2CF2CF2)-.

[0050] In the above formula (f16), f1 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 a1, b1, c1, d1, e1, and f1 is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0051] In one embodiment, the R F11 is a group represented by the above formula (f11).

[0052] In one embodiment, the R F11 is a group represented by the above formula (f12).

[0053] In one embodiment, the R F11 is a group represented by the above formula (f13) or (f14).

[0054] In one embodiment, the R F11 is a group represented by the above formula (f13).

[0055] In one embodiment, the R F11 is a group represented by the above formula (f14).

[0056] In one embodiment, the R F11 is a group represented by the above formula (f15).

[0057] In one embodiment, the R F11 is a group represented by the above formula (f16).

[0058] In one embodiment, the R F11 is a group represented by the above formula (f11), (f12), (f15) or (f16).

[0059] In one embodiment, the R F11 is a group represented by the above formula (f11), (f12), or (f16).

[0060] Above R F11 In the formula, the ratio of e1 to f1 (hereinafter referred to as "e / f ratio") is, for example, 0.1 or more and 10 or less, preferably 0.2 or more and 5 or less, more preferably 0.2 to 2, even more preferably 0.2 or more and 1.5 or less, still more preferably 0.2 or more and less than 0.9, and particularly preferably 0.2 or more and 0.85 or less. When the e / f ratio is within the above range, the stability of the obtained fluorine-containing compound is improved. Here, f1 is an integer of 1 or more.

[0061] In one embodiment, R F11In the formula, the e / f ratio is preferably 1.0 or more, for example, 1.1 or more, or may be 1.3 or more. F11 In the formula, the e / f ratio is preferably 10.0 or less, 9.0 or less, more preferably 5.0 or less, even more preferably 2.0 or less, and particularly preferably 1.5 or less. F11 In the formula, the e / f ratio is, for example, 1.0 to 10.0, specifically 1.0 to 5.0, more specifically 1.0 to 2.0, and even more specifically 1.0 to 1.5.

[0062] In one embodiment, R F11 In the formula, the e / f ratio may be in the range of 1.0 to 1.2.

[0063] In one embodiment, R F11 In the formula, the e / f ratio is less than 1.0, and may be, for example, less than 0.9, 0.8 or less, or 0.7 or less. F11 In the formula, the e / f ratio is preferably 0.2 or more, more preferably 0.3 or more, even more preferably 0.4 or more, and particularly preferably 0.5 or more. F11 In the formula, the e / f ratio is, for example, 0.2 or more and less than 0.9, specifically 0.4 or more and 0.8 or less, and more specifically 0.5 or more and 0.7 or less.

[0064] In one embodiment, R F11 In the formula, d1 is preferably an integer of 1 or more, more preferably 3 or more, and even more preferably 6 or more, and may be 200 or less, 120 or less, 60 or less, or 54 or less. In this embodiment, d1 may be 1 to 200, 3 to 120, 3 to 60, or 6 to 60.

[0065] In one embodiment, R F11 teeth, -(OC3F6) d1 -(OC2F4) e1 - (f11) [In the formula, d1 is an integer of 3 to 60, and preferably an integer of 6 to 54; e1 is 1; and OC3F6 and OC2F4 are linear.] It is a group represented by the following formula:

[0066] In one embodiment, R F11 teeth, -(OC3F6) d1 -(OC2F4) e1 - (f11) [In the formula, d1 is an integer of 3 to 120, preferably an integer of 6 to 60; e1 is 1; and each of OC3F6 and OC2F4 has a branched chain.] For example, in formula (f11), the repeating unit is represented by -OCF(CF3)CF2-.

[0067] Above R F11 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, and more preferably 2,000 to 10,000. F11 The number average molecular weight of 19 The value is measured by F-NMR.

[0068] In another embodiment, R F11 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.

[0069] In another embodiment, R F11 The number average molecular weight of the moiety can be from 4,000 to 30,000, preferably from 5,000 to 10,000, and more preferably from 6,000 to 10,000.

[0070] ·R F12 -(C s R e1 2s ) s1 -(R d )s2 - (f2)

[0071] R e1 are each independently a hydrogen atom, a fluorine atom, or a chlorine atom. R d are each independently an arylene group optionally substituted with a fluorine atom. However, R d or R e1 At least one of these is a fluorine atom. The arylene group is a divalent organic group obtained by removing two hydrogen atoms from the ring structure of an aromatic hydrocarbon group. An example of an arylene group is a phenylene group.

[0072] In one embodiment, R e1 is a fluorine atom.

[0073] In one embodiment, -C s R e1 2s -In all R e1 is substituted with a fluorine atom, i.e., -C s R e1 2s - is a perfluoroalkylene group, i.e., -(C s F 2s )-.

[0074] In one embodiment, R d (Specifically, R d At least some of the hydrogen atoms in R d is an arylene group substituted with a fluorine atom.

[0075] In one embodiment, R d In this formula, all hydrogen atoms are replaced with fluorine atoms.

[0076] In one embodiment, R F12In the formula (I), the arylene group is a phenylene group. The phenylene group may have a bonding position at any of the ortho, meta, or para positions. In one embodiment, the phenylene group has a bonding position at the para position.

[0077] In one embodiment, R F12 In the formula (I), all hydrogen atoms of the phenylene group are substituted with fluorine atoms.

[0078] s is an integer from 1 to 10.

[0079] s1 is an integer of 0 or more, and s2 is an integer of 0 or more. The sum of s1 and s2 is 1 or more. The repeating units enclosed in parentheses with s1 or s2 may be present in any order in the formula.

[0080] In one embodiment, s1 is an integer of 0 to 20, and s2 is an integer of 0 to 10. The sum of s1 and s2 is 1 or more.

[0081] R Si are each independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a silicon atom bonded to a monovalent organic group. Si contains a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto.

[0082] R Si is preferably a group represented by the following formula (S1): [ka]

[0083] R a1 are each independently -Z 1 -SiR 41 r1 R 42 r2 R 43 r3 is.

[0084] Z 1are each independently an oxygen atom or a divalent organic group. 1 The structure written as 41 r1 R 42 r2 R 43 r3 )

[0085] In a preferred embodiment, Z 1 is a divalent organic group.

[0086] In a preferred embodiment, Z 1 is Z 1 That is, in the formula (S1), (Si-Z) does not include those which form a siloxane bond with the Si atom to which it is bonded. 1 —Si) does not contain a siloxane bond.

[0087] Above Z 1 is preferably C 1-6 Alkylene group, -(CH2) z1 -O-(CH2) z2 - (wherein z1 is an integer of 0 to 6, for example, an integer of 1 to 6, and z2 is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH2) z3 -phenylene-(CH2) z4 - (wherein z3 is an integer of 0 to 6, for example, an integer of 1 to 6, and z4 is an integer of 0 to 6, for example, an integer of 1 to 6). 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 with one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0088] In a preferred embodiment, Z 1 is C 1-6 Alkylene group or (CH2) z3 -phenylene-(CH2) z4-, preferably -phenylene-(CH2) z4 -It is. Z 1 is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0089] In another preferred embodiment, Z 1 is C 1-6 Alkylene group or (CH2) z1 -O-(CH2) z2 -It is.

[0090] In another preferred embodiment, Z 1 is C 1-6 is an alkylene group, preferably C 1-3 In one embodiment, Z is an alkylene group. 1 can be -CH2CH2CH2-. In another embodiment, Z 1 can be -CH2CH2-.

[0091] Above R 41 independently in each occurrence -Z 1’ -SiR 41’ r1’ R 42’ r2’ R 43’ r3’ is.

[0092] Above Z 1’ In each occurrence, each independently represents an oxygen atom or a divalent organic group. 1’ The structure written as 41’ r1’ R 42’ r2’ R 43’ r3’ )

[0093] In a preferred embodiment, Z 1’ is a divalent organic group.

[0094] In a preferred embodiment, Z 1’ is Z 1’That is, in the formula (S1), (Si-Z) does not include those which form a siloxane bond with the Si atom to which it is bonded. 1’ —Si) does not contain a siloxane bond.

[0095] Above Z 1’ is preferably C 1-6 Alkylene group, -(CH2) z1’ -O-(CH2) z2’ - (wherein z1' is an integer of 0 to 6, for example, an integer of 1 to 6, and z2' is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH2) z3’ -phenylene-(CH2) z4’ - (wherein z3' is an integer of 0 to 6, for example, an integer of 1 to 6, and z4' is an integer of 0 to 6, for example, an integer of 1 to 6). 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 with one or more substituents selected from alkynyl groups, but is preferably unsubstituted. For example, the sum of z1' and z2' may be 1 or more, and the sum of z3' and z4' may be 1 or more.

[0096] In a preferred embodiment, Z 1’ is C 1-6 Alkylene group or (CH2) z3’ -phenylene-(CH2) z4’ -, preferably -phenylene-(CH2) z4’ -It is. Z 1’ is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0097] In another preferred embodiment, the Z 1’ is C 1-6 is an alkylene group, preferably C 1-3 In one embodiment, Z is an alkylene group. 1’ can be -CH2CH2CH2-. In another embodiment, Z 1’can be -CH2CH2-.

[0098] Above R 41’ independently in each occurrence -Z 1” -SiR 41” r1” R 42” r2” is.

[0099] Above Z 1” is independently in each occurrence an oxygen atom or a divalent organic group.

[0100] Z 1” In each occurrence, each independently represents an oxygen atom or a divalent organic group. 1” The structure written as 41” r1” R 42” r2” )

[0101] In a preferred embodiment, Z 1” is a divalent organic group.

[0102] In a preferred embodiment, Z 1” is Z 1” That is, in the formula (S1), (Si-Z) does not include those which form a siloxane bond with the Si atom to which it is bonded. 1” —Si) does not contain a siloxane bond.

[0103] Above Z 1” is preferably C 1-6 Alkylene group, -(CH2) z1” -O-(CH2) z2” - (wherein z1" is an integer of 0 to 6, for example, an integer of 1 to 6, and z2" is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH2) z3” -phenylene-(CH2) z4” - (wherein z3" is an integer of 0 to 6, for example, an integer of 1 to 6, and z4" is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6The 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 with one or more substituents selected from alkynyl groups, but is preferably unsubstituted. For example, the sum of z1" and z2" may be 1 or more, and the sum of z3" and z4" may be 1 or more.

[0104] In a preferred embodiment, Z 1” is C 1-6 Alkylene group or (CH2) z3” -phenylene-(CH2) z4” -, preferably -phenylene-(CH2) z4” -It is. Z 1” is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0105] In another preferred embodiment, the Z 1” is C 1-6 Alkylene group, preferably C 1-3 In one embodiment, Z is an alkylene group. 1” can be -CH2CH2CH2-. In another embodiment, Z 1” can be -CH2CH2-.

[0106] R 41” are each independently a hydroxyl group or a hydrolyzable group.

[0107] Above R 41” is preferably each independently a hydrolyzable group. The hydrolyzable group has the same meaning as defined above.

[0108] R 42” are each independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0109] Above R 42” In the formula, the monovalent organic group is preferably C1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0110] The above r1"s are each independently an integer of 0 to 3; the above r2"s are each independently an integer of 0 to 3. The sum of r1" and r2" is (SiR 41” r1” R 42” r2” ) units, it is 3.

[0111] r1” is (SiR 41” r1” R 42” r2” ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.

[0112] Above R 42’ are each independently a hydroxyl group or a hydrolyzable group.

[0113] R 42’ is preferably each independently a hydrolyzable group. The hydrolyzable group has the same meaning as defined above.

[0114] Above R 43’ are each independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0115] Above R 43’ In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0116] The above r1's are each independently an integer of 0 to 3; the above r2's are each independently an integer of 0 to 3; and the above r3's are each independently an integer of 0 to 3. The sum of r1', r2', and r3' is (SiR 41’ r1’ R42’ r2’ R 43’ r3’ ) units is 3.

[0117] In one embodiment, r1' is 0.

[0118] In one embodiment, r1′ is (SiR 41’ r1’ R 42’ r2’ R 43’ r3’ ) units may each independently be an integer of 1 to 3, an integer of 2 to 3, or 3. In a preferred embodiment, r1′ is 3.

[0119] In one embodiment, r2' is (SiR 41’ r1’ R 42’ r2’ R 43’ r3’ ) units are each independently an integer of 1 to 3, preferably an integer of 2 or 3, and more preferably 3.

[0120] In one embodiment, r2' is 0 and r3' is (SiR 41’ r1’ R 42’ r2’ R 43’ r3’ ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0121] Above R 42 are each independently a hydroxyl group or a hydrolyzable group.

[0122] R 42 is preferably each independently a hydrolyzable group. The hydrolyzable group has the same meaning as defined above.

[0123] Above R 43 are each independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0124] Above R 43 In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0125] The above r1's are each independently an integer of 0 to 3; the above r2's are each independently an integer of 0 to 3; and the above r3's are each independently an integer of 0 to 3. The sum of r1, r2, and r3 is (SiR 41 r1 R 42 r2 R 43 r3 ) units is 3.

[0126] In one embodiment, r1 is 0.

[0127] In one embodiment, r1 is (SiR 41 r1 R 42 r2 R 43 r3 ) units may each independently be an integer of 1 to 3, an integer of 2 to 3, or 3. In a preferred embodiment, r1 is 3.

[0128] In one embodiment, r2 is (SiR 41 r1 R 42 r2 R 43 r3 ) units are each independently an integer of 1 to 3, preferably an integer of 2 or 3, and more preferably 3.

[0129] In one embodiment, r1 is 0 and r2 is (SiR 41 r1 R 42 r2 R 43 r3 ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0130] Above R b1 are each independently a hydroxyl group or a hydrolyzable group.

[0131] Above R b1 is preferably each independently a hydrolyzable group. The hydrolyzable group has the same meaning as defined above.

[0132] Above R c1 are each independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.

[0133] Above R c1 In the formula, the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0134] Each of the k1's is independently an integer of 0 to 3; each of the l1's is independently an integer of 0 to 3; and each of the m1's is independently an integer of 0 to 3. The sum of k1, l1, and m1 is (SiR a1 k1 R b1 l1 R c1 m1 ) units is 3.

[0135] In one embodiment, k1 is (SiR a1 k1 R b1 l1 R c1 m1 ) units are each independently an integer of 1 to 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.

[0136] In one embodiment, (SiR a1 k1 R b1 l1 R c1 m1) Independently for each unit, k1 is 1 or 2, l1 is 2 or 1, and m1 is 0.

[0137] In one embodiment, (SiR a1 k1 R b1 l1 R c1 m1 ) Independently for each unit, k1 is 1 or 2, l1 is 0, and m1 is 2 or 1.

[0138] In one embodiment, k1 is 0. In other words, -SiR a1 k1 R b1 l1 R c1 m1 The group represented by is -SiR b1 l1 R c1 m1 and the sum of l1 and m1 is 3. However, in this embodiment, at least one Si atom bonded to a hydroxyl group or a hydrolyzable group is present in the terminal portion of formula (A1) and formula (A2). The above l1 is preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 3, each occurrence being independent.

[0139] In one embodiment, k1 is 0 and l1 is preferably 2 or 3, more preferably k1 is 0 and l1 is 3.

[0140] In formula (S1), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group. That is, the group represented by formula (S1) is -SiR b1 l1 R c1 m1 (wherein l1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and the sum of l1 and m1 is 3), -SiR 42 r2 R 43 r3(wherein r2 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and the sum of r2 and r3 is 3), -SiR 42’ r2’ R 43’ r3’ (wherein r2' is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and the sum of r2' and r3' is 3), or -SiR 41” r1” R 42” r2” (wherein r1″ is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and the sum of r1″ and r2″ is 3).

[0141] In a preferred embodiment, there are at least two Si atoms bonded to hydroxyl groups or hydrolyzable groups in the terminal portions of formula (A1) and formula (A2).

[0142] In a preferred embodiment, in formula (S1), R a1 When present, at least one, preferably all, R a1 In the formula, r2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0143] In a preferred embodiment, in formula (S1), R 41 When present, at least one, preferably all, R 41 In the formula, r2′ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0144] In a preferred embodiment, in formula (S1), R 41’ When present, at least one, preferably all, R 41’ In the formula, r1″ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0145] In a preferred embodiment, in formula (S1), k1 is 2 or 3, preferably 3; r1 is 0; and r2 is 2 or 3, preferably 3.

[0146] In one embodiment, the fluorine atom-containing silane compound is a compound represented by formula (A1).

[0147] In one embodiment, the fluorine atom-containing silane compound is a compound represented by formula (A2).

[0148] The fluorine atom-containing silane compound represented by the formula (A1) or (A2) is not particularly limited, but may be 5×10 2 ~1×10 5 Within this range, it is preferable from the viewpoint of friction durability that the average molecular weight is 2,000 to 32,000, more preferably 2,500 to 12,000. Note that the "average molecular weight" refers to a number average molecular weight, and the "average molecular weight" is 19 The value is measured by F-NMR.

[0149] (Method of producing fluorine atom-containing silane compound) The fluorine atom-containing silane compound can be produced by a method including the following steps: The fluorine atom-containing silane compound may be produced by other methods without being limited to the following steps.

[0150] Process (A): Formula (B1) or Formula (B2): [ka] A compound represented by the formula (wherein R F1 , R F2 is as defined above) to form a compound represented by the formula HSiM3 (wherein each M is independently a halogen atom or C 1-6 alkoxy group) to form a compound of formula (B13) or (B23): [ka] obtaining a compound represented by the formula: Process (B): A compound represented by formula (B13) or (B23) is reacted with a compound represented by formula: Hal-J-Z'-CH=CH2 (wherein Z' represents a bond or a divalent organic group, J represents Mg, Cu, Pd or Zn, and Hal represents a halogen atom), and, if desired, Formula: Y h L (wherein Y is, for example, R b1 or R c1 wherein L represents a group capable of bonding to Y, and h is an integer of 1 to 3. with a compound represented by formula (B14) or (B24): [ka] (In the formula, R F1 and R F2 has the same meaning as above, Y and Z' have the same meaning as above, and k' is an integer of 1 to 3. obtaining a compound represented by the formula: Process (C): A compound represented by formula (B14) or formula (B24), Formula: HSiM3 (wherein M is as defined above) and / or Formula:R 1 i L'(where R 1 is R 42 or R 43 and L' is R 1 represents a group capable of bonding to, and i is an integer of 1 to 3. and optionally a compound represented by Formula:R 2’ j L” (in the formula, R 2’ is C 1-22 represents an alkyl group, and L" represents R 2’ represents a group capable of bonding to, and j is an integer of 1 to 3. a step of reacting the compound represented by the formula: A method is provided that includes:

[0151] The above steps (A) to (C) can be carried out based on, for example, JP 2014-218639 A.

[0152] The compound represented by formula (B1) or formula (B2) can be produced by a method comprising the following step (D):

[0153] Process (D): Formula (B31) or Formula (B41): [ka] By adding a methylenylating reagent to a compound represented by formula (B1) or formula (B2): [ka] A forming step of forming a compound represented by the formula:

[0154] The compound represented by formula (B31) and the compound represented by formula (B41) may be represented as hydrates of the following compounds, respectively. [ka]

[0155] R F1 and R F2 are the same as above.

[0156] Examples of the methylenylation reagent include Wittig reagent, Horner-Wadsworth-Emmons reagent, Peterson reagent, Tebbe reagent, Petasis reagent, Julia-Koclenski reagent, etc., and preferably the Wittig reagent is used.

[0157] Wittig reagent, Ph3PR 12 Hal can be treated with a base to dehydrohalogenate it, thereby obtaining the ylide Ph3P. + C - R 12 and phosphorane Ph3P=CR 12 A resonance structure is formed with: where Ph is a phenyl group; R 12R is an alkyl group which may have a heteroatom interposed therebetween, a divalent organic group having a terminal carbon-carbon double bond, etc.; Hal is a halogen atom (e.g., F, Cl, Br, I). 12 For example, C 1-3 Alkyl group or C 2-3 An alkylene group can be mentioned. Ph3PR 12 Examples of Hal include Ph3PCH3Br, Ph3PCH3Cl, Ph3PCH2CH3Br, Ph3PCH2CH2CH3Br, and Ph3PCH2CH=CH2Br. Examples of the base include potassium t-butoxide, butyllithium, phenyllithium, potassium hexamethyldisilazane, and the like.

[0158] The concentration of the methylenylating reagent can be adjusted appropriately, but for example, it can be added in an amount of 1 to 10 times per 1 mol of the carbonyl groups of the formula (B32) and the formula (B42).

[0159] Step (D) can be carried out, if necessary, at 0 to 80° C. The reaction time is not particularly limited, but is, for example, 0.5 to 48 hours.

[0160] Step (D) can be carried out at room temperature. The reaction time is not particularly limited, but is, for example, 0.5 to 48 hours. Heating may be performed as necessary.

[0161] In step (D), at least one of the compound represented by formula (B31) and the compound represented by formula (B41) can be added to the solution as appropriate, for example, in an amount of 1 to 1,000 g / L relative to the total solution.

[0162] Step (D) is preferably carried out in a solution, and examples of solvents that can be used include methylene chloride, tetrahydrofuran, toluene, Novec HFE7200, Novec HFE7300, and 1,3-bis(trifluoromethyl)benzene.

[0163] In step (D), at least one of the compound represented by formula (B31) and the compound represented by formula (B41) can be added to the solution as appropriate, for example, in an amount of 1 to 1,000 g / L relative to the total solution.

[0164] The compound represented by formula (B31) or formula (B41) can be produced, for example, according to the following step (E) or step (F).

[0165] Process (E) Process (E1): Formula (B11) or Formula (B21): [ka] A reaction step of forming an ester bond by a dehydration condensation reaction between a compound represented by the formula: and an alcohol; and Process (E2): A reaction step in which the ester bond is reduced using a metal hydride reagent.

[0166] Step (E1) is orthoformate HCR 11 3, where R 11 are each independently an alkoxide (e.g., methoxide). Step (E1) can be carried out, if necessary, at 0 to 100° C. The reaction time is not particularly limited, but is, for example, 1 to 20 hours.

[0167] Step (E2) can be carried out using a metal hydride reagent, for example, diisobutylaluminum hydride. Step (E2) can be carried out at room temperature. Here, room temperature refers to a temperature in the range of 0 to 30° C. The reaction time is not particularly limited, but is, for example, 1 to 48 hours. Heating may be performed as necessary.

[0168] Process (F) Process (F1): Formula (B11) or Formula (B21): [ka] a reduction reaction step of reducing the compound represented by the formula (I) by adding a reducing agent to the compound; Process (F2): Formula (B12) or Formula (B22) obtained in the above step: [ka] an oxidation step of adding an oxidizing agent to a compound represented by the formula:

[0169] A reducing agent can be used in the reduction reaction of step (F1), and examples of the reducing agent include metal hydride reagents such as NaBH4 and LiAlH4, and hydrogenation in the presence of a Pd catalyst.

[0170] The reduction reaction in step (F1) can be carried out using, for example, NaBH4.

[0171] In step (F2), a hypervalent iodine compound such as Dess-Martin periodinane (1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3-(1H)-one) may be used as an oxidizing agent.

[0172] (composition) The fluorine atom-containing silane compound represented by formula (A1) or formula (A2) can be used as a composition.

[0173] The content of the fluorine atom-containing silane compound may be, for example, 10% by mass or less, or may be 3% by mass or less, relative to the composition, and the content may be, for example, 0.5% by mass or more, or may be 0.01% by mass or more.

[0174] The composition can impart water repellency, oil repellency, antifouling properties, surface slip properties, and friction durability to a substrate, and can be suitably used as, but not limited to, a surface treatment agent for treating the surface of a substrate, an antifouling coating agent, or a waterproof coating agent.

[0175] The composition may contain a fluorine atom-containing silane compound represented by formula (A1) and a fluorine atom-containing silane compound represented by formula (A2).

[0176] In one embodiment, the lower limit of the ratio (molar ratio) of the fluorine atom-containing silane compound represented by formula (A2) to the total of the fluorine atom-containing silane compounds represented by formula (A1) and formula (A2) may be preferably 0.001, more preferably 0.002, even more preferably 0.005, even more preferably 0.01, particularly preferably 0.02, and especially 0.05. The upper limit of the ratio (molar ratio) of the fluorine atom-containing silane compound represented by formula (A2) to the total of the fluorine atom-containing silane compounds represented by formula (A1) and formula (A2) may be preferably 0.70, more preferably 0.60, more preferably 0.50, even more preferably 0.40, and even more preferably 0.20 or 0.10. The ratio (molar ratio) of the fluorine atom-containing silane compound represented by formula (A2) to the total of the fluorine atom-containing silane compounds represented by formula (A1) and 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, or 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).

[0177] In one embodiment, the lower limit of the ratio (molar ratio) of the fluorine-containing silane compound represented by formula (A1) to the total of the fluorine-containing silane compounds represented by formula (A1) and formula (A2) may be preferably 0.001, more preferably 0.002, even more preferably 0.005, even more preferably 0.01, particularly preferably 0.02, and especially 0.05. The upper limit of the ratio (molar ratio) of the fluorine-containing silane compound represented by formula (A1) to the total of the fluorine-containing silane compounds represented by formula (A1) and formula (A2) may be preferably 0.70, more preferably 0.60, more preferably 0.50, even more preferably 0.40, and even more preferably 0.20 or 0.10. The ratio (molar ratio) of the fluorine atom-containing silane compound represented by formula (A1) to the total of the fluorine atom-containing silane compounds represented by formula (A1) and 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, or 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] The composition may further contain a solvent, a (non-reactive) fluoropolyether compound which may be understood as a fluorine-containing oil, preferably a PFPE compound (hereinafter collectively referred to as "fluorine-containing oil"), a (non-reactive) silicone compound which may be understood as a silicone oil (hereinafter referred to as "silicone oil"), a catalyst, a surfactant, a polymerization inhibitor, a sensitizer, etc.

[0179] Examples of the solvent include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, and ethyl 2-hydroxybutyrate. Esters such as ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, 2-heptanone; ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether ... Glycol ethers such as ethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, and ethylene glycol monoalkyl ether; alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, and tert-amyl alcohol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; and diethylene glycol monoethyl ether acetate.Examples of the solvent include fluorine-containing solvents such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethyl sulfoxide, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), Zeorora H, HFE7100, HFE7200, and HFE7300. Alternatively, examples include mixed solvents of two or more of these solvents.

[0180] The fluorine-containing oil is not particularly limited, but examples thereof include compounds represented by the following general formula (3) (PFPE compounds). Rf 5 -(OC4F8) a’ -(OC3F6) b’ -(OC2F4) c’ -(OCF2) d’ -Rf 6 ···(3) In the formula, Rf 5 is an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms (preferably, C 1―16 Rf represents a perfluoroalkyl group 6 is an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms (preferably, C 1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom, and Rf 5 and Rf 6 More preferably, each independently represents C 1-3 It is a perfluoroalkyl group. a', b', c', and d' respectively represent the number of four types of repeating units of the perfluoro(poly)ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, and the sum of a', b', c', and d' is at least 1, preferably 1 to 300, and more preferably 20 to 300. The order of occurrence of each repeating unit enclosed in parentheses with the subscript a', b', c', or d' is arbitrary in the formula. Of these repeating units, -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and (OCF2CF(C2F5))-, but is preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-, but is preferably -(OCF2CF2CF2)-. -(OC2F4)- may be either -(OCF2CF2)- or (OCF(CF3))-, but is preferably -(OCF2CF2)-.

[0181] Examples of the PFPE compound represented by the above general formula (3) include compounds represented by either of the following general formulas (3a) and (3b) (which may be one type or a mixture of two or more types): Rf 5 -(OCF2CF2CF2) b” -Rf 6 (3a) Rf 5 -(OCF2CF2CF2CF2) a” -(OCF2CF2CF2) b” -(OCF2CF2) c” -(OCF2) d” -Rf 6 (3b) In these formulas, Rf 5 and Rf 6is as defined above; in formula (3a), b" is an integer of 1 or more and 100 or less; in formula (3b), a" and b" are each independently an integer of 0 or more and 30 or less, and c" and d" are each independently an integer of 1 or more and 300 or less. The order of occurrence of each repeating unit enclosed in parentheses with the subscripts a", b", c", and d" is arbitrary in the formula.

[0182] From another perspective, fluorine-containing oils are those represented by the general formula Rf 3 -F(where Rf 3 is C 5-16 It may be a compound represented by the formula: wherein R is a perfluoroalkyl group.) It may also be a chlorotrifluoroethylene oligomer.

[0183] The fluorine-containing oil may have an average molecular weight of 500 to 10,000. The molecular weight of the fluorine-containing oil can be measured using gel permeation chromatography (GPC).

[0184] The fluorinated oil may be contained in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass, relative to the composition of the present disclosure (e.g., surface treatment agent). In one embodiment, the composition of the present disclosure is substantially free of fluorinated oil. "Substantially free of fluorinated oil" means that the composition does not contain any fluorinated oil at all, or may contain a very small amount of fluorinated oil.

[0185] The fluorine-containing oil contributes to improving the surface slip properties of the layer formed by the composition (for example, surface treatment agent) of the present disclosure.

[0186] In one embodiment, the compound represented by formula (A2) may be contained in an amount of, for example, 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, based on the total of the fluorine atom-containing silane compound represented by formula (A1), the fluorine atom-containing silane compound represented by formula (A2), and the fluorine oil. The fluorine atom-containing silane compound represented by formula (A2) may be contained in an amount of, for example, 1 to 70 mol%, or 5 to 50 mol%, based on the total of the fluorine atom-containing silane compound represented by formula (A1), the fluorine atom-containing silane compound represented by formula (A2), and the fluorine oil.

[0187] In one embodiment, the fluorinated oil may be contained in an amount of, for example, 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, based on the total of the fluorine atom-containing silane compound represented by formula (A1), the fluorine atom-containing silane compound represented by formula (A2), and the fluorinated oil. The fluorinated oil may be contained in an amount of, for example, 0.001 to 50 mol %, or 0.01 to 40 mol %, based on the total of the fluorine atom-containing silane compound represented by formula (A1), the fluorine atom-containing silane compound represented by formula (A2), and the fluorinated oil.

[0188] In one embodiment, the fluorine atom-containing silane compound represented by formula (A2) is preferably contained in an amount of 0.001 to 70 mol % and the fluorine atom-containing oil is preferably contained in an amount of 0.001 to 50 mol % relative to the total of the fluorine atom-containing silane compound represented by formula (A1), the fluorine atom-containing silane compound represented by formula (A2), and the fluorine oil, more preferably contained in an amount of 0.01 to 60 mol % and the fluorine atom-containing silane compound represented by formula (A2) is preferably contained in an amount of 0.01 to 40 mol %, and even more preferably contained in an amount of 0.1 to 50 mol % and the fluorine atom-containing silane compound represented by formula (A2) is preferably contained in an amount of 0.1 to 30 mol %.

[0189] The silicone oil may be, for example, a linear or cyclic silicone oil having 2,000 or less siloxane bonds. The linear silicone oil may be a so-called straight silicone oil or a modified silicone oil. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil.

[0190] In the composition of the present disclosure, such silicone oil may be contained in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, relative to a total of 100 parts by mass of the fluorine atom-containing silane compounds of the present disclosure (the total of these when two or more types are used, the same applies hereinafter).

[0191] Silicone oil contributes to improving the surface slip properties of the layer formed from the composition of the present disclosure.

[0192] Examples of the catalyst include acids (eg, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), and transition metals (eg, Ti, Ni, Sn, etc.).

[0193] The catalyst promotes the hydrolysis and dehydration condensation of the fluorine atom-containing silane compound of the present disclosure, and promotes the formation of a layer formed by the composition (for example, surface treatment agent) of the present disclosure.

[0194] In addition to the above, other components include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane.

[0195] (pellet) The compositions of the present disclosure can be impregnated into porous materials, such as porous ceramic materials, metal fibers, such as steel wool, and formed into pellets, which can be used, for example, in vacuum deposition.

[0196] In one embodiment, the compositions of the present disclosure are used for wet coating applications.

[0197] (Goods) The articles of the present disclosure are described below.

[0198] The article of the present disclosure includes a substrate and a layer (surface treatment layer) formed on the surface of the substrate from a composition (surface treatment agent) containing the fluorine atom-containing silane compound of the present disclosure.

[0199] Substrates that can be used in the present disclosure may be made of any appropriate material, such as glass, resin (which may be a natural or synthetic resin, for example, a common plastic material, and may be in the form of a plate, film, or other form), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., building materials, etc.

[0200] For example, if the article to be manufactured is an optical component, the material constituting the surface of the substrate may be a material for optical components, such as glass or transparent plastic. Furthermore, if the article to be manufactured is an optical component, some layer (or film), such as a hard coat layer or an antireflection layer, may be formed on the surface (outermost layer) of the substrate. The antireflection layer may be either a single-layer antireflection layer or a multilayer antireflection layer. Examples of inorganic materials that can be used in the antireflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, YO3, SnO2, MgF2, and WO3. These inorganic materials may be used alone or in combination (e.g., as a mixture) of two or more of them. When a multilayer antireflection layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the product to be manufactured is an optical glass component for a touch panel, a transparent electrode, such as a thin film made of indium tin oxide (ITO) or indium zinc oxide, may be provided on a portion of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, etc., depending on the specific specifications.

[0201] The shape of the substrate is not particularly limited. The surface region of the substrate on which the surface treatment layer is to be formed may be at least a part of the substrate surface, and may be appropriately determined depending on the application and specific specifications of the article to be manufactured.

[0202] Such substrates may be made of materials that inherently contain hydroxyl groups, at least on their surface. Examples of such materials include glass, metals (especially base metals), ceramics, and semiconductors, which form natural or thermal oxide films on their surfaces. Alternatively, for materials such as resins, which do not inherently contain hydroxyl groups but have insufficient hydroxyl groups, or which do not inherently contain hydroxyl groups, pretreatment can be performed on the substrate to introduce or increase the number of hydroxyl groups on the substrate surface. Examples of such pretreatments include plasma treatment (e.g., corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the substrate surface and can also be used to clean the substrate surface (remove foreign matter, etc.). Another example of such pretreatment is a method in which an interfacial adsorbent having carbon-carbon unsaturated bond groups is first formed in the form of a monomolecular film on the substrate surface by the Langmuir-Blodgett method (LB method) or chemical adsorption, followed by cleavage of the unsaturated bonds in an atmosphere containing oxygen, nitrogen, or the like.

[0203] Alternatively, at least the surface portion of such a substrate may be made of a material containing another reactive group, such as a silicone compound having one or more Si—H groups, or an alkoxysilane.

[0204] Next, a layer of the composition of the present disclosure (for example, a surface treatment agent) is formed on the surface of the substrate, and this layer is post-treated as needed, thereby forming a layer from the composition of the present disclosure.

[0205] The layer formation of the surface treatment agent of the present disclosure can be carried out by applying the above-mentioned composition to the surface of a substrate so as to coat the surface. The coating method is not particularly limited. For example, a wet coating method or a dry coating method can be used.

[0206] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.

[0207] Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum deposition) include resistance heating, electron beam, high frequency heating using microwaves, ion beam, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0208] Furthermore, coating by atmospheric pressure plasma method is also possible.

[0209] When using the wet coating method, the composition of the present disclosure may be diluted with a solvent and then applied to the surface of a substrate. From the viewpoint of the stability of the composition of the present disclosure and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., CF 13CH2CH3 (e.g., Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeorora (registered trademark) H manufactured by Zeon Corporation); hydrofluoroethers (HFEs) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), 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 Asahi Glass Co., Ltd.). 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. Preferably, the solvent used in the wet coating method is the same as the solvent used in the composition of the present disclosure.

[0210] When the dry coating method is used, the composition of the present disclosure may be subjected to the dry coating method as it is, or may be diluted with the above-mentioned solvent before being subjected to the dry coating method.

[0211] The composition of the present disclosure can be effectively used in wet coating methods, particularly spray coating, because it can be easily dispersed.

[0212] The layer formation of the composition is preferably carried out so that the composition of the present disclosure is present in the layer together with a catalyst for hydrolysis and dehydration condensation.Conveniently, in the case of a wet coating method, the composition of the present disclosure may be diluted with a solvent, and then a catalyst may be added to the diluted solution of the composition of the present disclosure just before applying it to the surface of a substrate.In the case of a dry coating method, the composition of the present disclosure to which the catalyst has been added may be directly vapor-deposited (usually vacuum vapor-deposited), or a pellet-shaped material impregnated with the surface treatment agent of the present disclosure to which the catalyst has been added may be vapor-deposited (usually vacuum vapor-deposited) on a porous metal such as iron or copper.

[0213] Any suitable acid or base can be used as the catalyst. Examples of acid catalysts that can be used include acetic acid, formic acid, and trifluoroacetic acid. Examples of base catalysts that can be used include ammonia and organic amines.

[0214] As described above, a layer derived from the composition of the present disclosure is formed on the surface of the substrate, and an article of the present disclosure is manufactured. The layer obtained thereby has both high surface slippage and high friction durability. In addition to high friction durability, depending on the composition of the surface treatment agent used, the layer may also have water repellency, oil repellency, antifouling properties (for example, preventing adhesion of stains such as fingerprints), waterproof properties (preventing water penetration into electronic components, etc.), surface slippage (or lubricity, for example, ease of wiping off stains such as fingerprints and excellent tactile feel), etc., and can be suitably used as a functional thin film.

[0215] That is, the present disclosure further relates to an optical material having the above composition (for example, a surface treatment layer) as the outermost layer.

[0216] Preferred examples of the optical material include optical materials related to displays and the like, such as those exemplified below, as well as a wide variety of other optical materials: for example, displays such as cathode ray tubes (CRTs; for example, personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, vacuum fluorescent displays (VFDs), and field emission displays (FEDs), or protective plates for such displays, or displays whose surfaces have been treated with an anti-reflection film.

[0217] The article having a layer obtained by the present disclosure may be, but is not particularly limited to, an optical member. Examples of optical members include lenses for eyeglasses and the like; front protective plates, anti-reflection plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; and the display surfaces of watches and clocks.

[0218] Additionally, the article having a layer obtained according to the present disclosure may be a medical device or medical material.

[0219] Furthermore, the article having the layer obtained by the present disclosure may be an automobile interior or exterior component. Examples of exterior components include windows, light covers, and exterior camera covers. Examples of interior components include instrument panel covers, navigation system touch panels, and decorative interior components.

[0220] The thickness of the layer is not particularly limited. In the case of optical members, the thickness of the layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, and preferably 1 to 15 nm, from the viewpoints of optical performance, surface smoothness, friction durability, and antifouling properties.

[0221] The fluorine atom-containing silane compound of the present disclosure, a composition containing the fluorine atom-containing silane compound, an article having a substrate and a mold formed from the composition, a method for producing a fluorine atom-containing silane compound, etc. The fluorine atom-containing silane compound of the present disclosure, the composition containing the fluorine atom-containing silane compound, the substrate and the composition are not limited to the examples given above, and various modifications in form and details are possible without departing from the spirit and scope of the claims. [Example]

[0222] The present disclosure will be described below with reference to examples, but the present disclosure is not limited to the following examples.

[0223] (Synthesis Example 1) 2.5 g of methyltriphenylphosphonium bromide was dissolved in 5.0 g of tetrahydrofuran and cooled on ice. 6.7 ml of potassium t-butoxide (1.0 M / L tetrahydrofuran solution) was added and stirred for 20 minutes. This solution was added to ice-cooled CFO-(CFCFO) m -(CF2O) n 10.0 g of -CF2CH(OH)2 (m ≒ 25, n ≒ 23) was slowly added to a solution of 20.0 g of 1,3-bis(trifluoromethyl)benzene, and the mixture was stirred at room temperature for 20 hours. 19 F-NMR reveals that CF3O (CF2CF2O) m -(CF2O) n The chemical shift of the aldehyde group β-position -CF2- in CF2CH(OH)2 shifts downfield, and 1 This was confirmed by the generation of a vinyl group peak by H-NMR. Water was added to the reaction solution, and the lower phase was separated. The upper phase was extracted with 1,3-bis(trifluoromethyl)benzene, combined with the lower phase, washed twice with water, dried over magnesium sulfate, and concentrated. The resulting concentrate was purified using a flash column to obtain 7.8 g of polyether group-containing compound (A). Polyether group-containing compound (A): [ka] (m≒25, n≒23)

[0224] (Synthesis Example 2) 3.0 g of the polyether group-containing compound (A) obtained in Synthesis Example 1 was dissolved in 6 g of 1,3-bis(trifluoromethyl)benzene, and 0.02 g of triacetoxymethylsilane and 0.04 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, followed by 0.8 g of trichlorosilane and stirring at 10°C for 30 minutes. The mixture was then heated to 80°C and stirred for 5 hours. The end point of the reaction was 1 The reaction mixture was confirmed by the disappearance of the vinyl group protons using H-NMR. After distilling off the volatiles under reduced pressure, the mixture was cooled with ice and 3.7 ml of allyl magnesium chloride (1.0 M / L tetrahydrofuran solution) was slowly added. The reaction mixture was returned to room temperature and stirred overnight. 3.0 ml of dehydrated methanol was added to the reaction mixture, which was then filtered through Celite. The lower phase was concentrated to obtain 3.0 g of polyether group-containing compound (B). Polyether group-containing compound (B): [ka] (m≒25, n≒23)

[0225] (Synthesis Example 3) 3.0 g of the polyether group-containing compound (B) obtained in Synthesis Example 2 was dissolved in 6 g of 1,3-bis(trifluoromethyl)benzene, and 0.02 g of triacetoxymethylsilane and 0.04 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added. Then, 0.8 g of trichlorosilane was added and stirred at 10°C for 30 minutes. The mixture was then heated to 65°C and stirred for 4 hours. After distilling off the volatiles under reduced pressure, a mixed solution of 0.1 g of methanol and 2.0 g of trimethyl orthoformate was added, and the mixture was heated to 60°C and stirred for 3 hours. The resulting mixture was then purified to obtain 2.9 g of the following fluorine atom-containing silane compound (C) having a terminal trimethoxysilyl group. Fluorine atom-containing silane compound (C): [ka] (m≒25, n≒23)

[0226] (Synthesis Example 4) CF3CF2CF2O-(CF2CF2CF2O) m The same procedures as in Synthesis Examples 1 to 3 were carried out except that 10.0 g of -CF2CF2CH(OH)2 (m 27) was used, to obtain 3.0 g of a fluorine atom-containing silane compound (D). Fluorine atom-containing silane compound (D): [ka] (m≒27)

[0227] (Synthesis Example 5) 3.0 g of the polyether group-containing compound (A) obtained in Synthesis Example 1 was dissolved in 6 g of 1,3-bis(trifluoromethyl)benzene, and 0.02 g of triacetoxymethylsilane and 0.04 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, followed by 0.8 g of trichlorosilane and stirring at 10°C for 30 minutes. The mixture was then heated to 80°C and stirred for 5 hours. The end point of the reaction was 1 The reaction mixture was confirmed by the disappearance of the vinyl group protons using H-NMR. After distilling off the volatiles under reduced pressure, the mixture was cooled with ice and 3.7 ml of vinyl magnesium chloride (1.0 M / L tetrahydrofuran solution) was slowly added. The reaction mixture was returned to room temperature and stirred overnight. 3.0 ml of dehydrated methanol was added to the reaction mixture, which was then filtered through Celite. The lower phase was concentrated to obtain 2.9 g of polyether group-containing compound (E). Polyether group-containing compound (E): [ka] (m≒25, n≒23)

[0228] (Synthesis Example 6) 2.0 g of the polyether group-containing compound (E) obtained in Synthesis Example 5 was dissolved in 4 g of 1,3-bis(trifluoromethyl)benzene, and 0.02 g of triacetoxymethylsilane and 0.03 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added. Then, 0.6 g of trichlorosilane was added and stirred at 10°C for 30 minutes. The mixture was then heated to 65°C and stirred for 4 hours. After distilling off the volatiles under reduced pressure, a mixed solution of 0.1 g of methanol and 2.0 g of trimethyl orthoformate was added, and the mixture was heated to 60°C and stirred for 3 hours. The resulting mixture was then purified to obtain 2.0 g of a fluorine atom-containing silane compound (F) having a terminal trimethoxysilyl group. Fluorine atom-containing silane compounds (F): [ka] (m≒25, n≒23)

[0229] Example 1 The fluorine atom-containing silane compound (C) obtained in Synthesis Example 3 above was dissolved in hydrofluoroether (Novec HFE-7200, manufactured by 3M) to a concentration of 0.1 mass % to prepare a surface treatment agent (1).

[0230] Example 2 The fluorine atom-containing silane compound (D) obtained in Synthesis Example 4 above was dissolved in hydrofluoroether (Novec HFE-7200, manufactured by 3M) to a concentration of 0.1 mass % to prepare a surface treatment agent (2).

[0231] Example 3 The fluorine atom-containing silane compound (F) obtained in Synthesis Example 6 above was dissolved in hydrofluoroether (Novec HFE-7200, manufactured by 3M) to a concentration of 0.1 mass % to prepare a surface treatment agent (3).

[0232] (Comparative Example 1) Comparative surface treatment agents (1) were prepared in the same manner as in Example 2, except that the following control compound (1) was used instead of the polyether group-containing compound (D). Control compound (1): [ka] (m≒25, n≒23)

[0233] (Formation of hardened film) Cured films were formed using each of the surface treatment agents (1) to (3) and the comparative surface treatment agent (1) as follows. The surface treatment agent or the comparative surface treatment agent was applied onto chemically strengthened glass (manufactured by Corning Incorporated, "Gorilla" glass, thickness 0.7 mm) using a spin coater. The spin coating conditions were 300 rpm for 3 seconds and 2000 rpm for 30 seconds. After coating, the glass was heated in a thermostatic chamber at 150°C for 30 minutes in the atmosphere to form a cured film.

[0234] (static contact angle) The static contact angle was measured using a fully automatic contact angle meter DropMaster 700 (manufactured by Kyowa Interface Science Co., Ltd.) by the following method. <Method for measuring static contact angle> The static contact angle was measured by dropping 2 μL of water or n-hexadecane from a microsyringe onto a horizontally placed substrate and taking a still image 1 second after the drop with a video microscope.

[0235] (Abrasion resistance evaluation of cured film) The abrasion resistance of the resulting cured film was evaluated as follows.

[0236] <Eraser abrasion resistance test> Using a rubbing tester (manufactured by Shinto Scientific Co., Ltd.), the water contact angle was measured every 2,500 rubs under the following conditions, and the test was continued until the contact angle reached 10,000 rubs or less than 100 degrees. The test environment conditions were 25°C and humidity 40% RH. Eraser: Rubber Eraser (Minoan) Ground contact area: 6mmφ Travel distance (one way): 30 mm Traveling speed: 3,600mm / min Load: 1kg / 6mmφ

[0237] The above evaluation results are shown in Table 1 below.

[0238] [Table 1]

[0239] (Weather resistance evaluation of cured film) The weather resistance of the resulting cured film was evaluated as follows.

[0240] <Accelerated weather resistance test> UV irradiation was performed using a UVB-313 lamp (manufactured by Q-Lab, irradiance 0.63 W / m at 310 nm). 2 ) was used, the distance between the lamp and the surface treatment layer of the substrate was set to 5 cm, and the temperature of the plate on which the substrate was placed was set to 63°C. When measuring the static contact angle of water, the substrate was temporarily removed and the surface treatment layer was wiped back and forth five times with Kimwipes (trade name, manufactured by Jujo Kimberly Co., Ltd.). Immediately afterwards, the static contact angle of water was measured.

[0241] The above evaluation results are shown in Table 2 below.

[0242] [Table 2]

[0243] As shown in Tables 1 and 2, it was found that the presence of CH2CH2 as the first linker resulted in the formation of a surface treatment layer with good friction durability and weather resistance. This is because the length of the first linker was very short and the bulk of the first linker was small, so that R F This is thought to be because the groups are densely packed together, which results in the surface treatment layer having greater resistance to abrasion and UV irradiation. [Industrial Applicability]

[0244] The present invention can be suitably used to form a surface treatment layer having better abrasion resistance and weather resistance on the surface of a wide variety of substrates, particularly on the surface of optical members that require transparency.

Claims

1. Formula (A1) or (A2): 【Chemistry 1】 [In the formula: R Ｆ１ is Rf １ -R Ｆ -O ｑ - and; R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ - and; Rf １ is a C optionally substituted by one or more fluorine atoms; １－１６ is an alkyl group; Rf ２ is a C optionally substituted by one or more fluorine atoms １－６ an alkylene group; R Ｆ are each independently a divalent fluorine atom-containing group; p is 0 or 1; Each q is independently 0 or 1; R Ｓｉ are each independently 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 At least one R Ｓｉ contains a Si atom to which a hydroxyl group or a hydrolyzable group is bonded. Fluorine atom-containing silane compound represented by the formula:

2. R Ｆ are each independently represented by the following formula (f1) or formula (f2): -(OC ｊ R ｅ ２ｊ ) ｊ１ -(OC ｈ R ｅ ２ｈ－２ ) ｈ１ - (f1) [In the formula: -OC ｊ R ｅ ２ｊ - each independently represents a repeating unit having a straight chain or a branched chain; -OC ｈ R ｅ ２ｈ－２ - each independently represents a repeating unit having a ring structure; R ｅ are each independently a hydrogen atom, a fluorine atom, or a chlorine atom; However, R Ｆ At least one R ｅ is a fluorine atom; j's are each independently an integer from 1 to 6; h is independently an integer from 1 to 7; j1 is an integer equal to or greater than 0; h1 is an integer equal to or greater than 0; the sum of j1 and h1 is greater than or equal to 1; The repeating units enclosed in parentheses with j1 or h1 may occur in any order in the formula.] -(C ｓ R ｅ１ ２ｓ ) ｓ１ -(R ｄ ) ｓ２ - (f2) [In the formula: Each s is independently an integer from 1 to 10; R ｅ１ are each independently a hydrogen atom, a fluorine atom, or a chlorine atom; R ｄ each independently represents an arylene group optionally substituted with a fluorine atom; However, R ｄ or R ｅ１ at least one of which is a fluorine atom; s1 is an integer equal to or greater than 0; s2 is an integer equal to or greater than 0; the sum of s1 and s2 is greater than or equal to 1; The order of occurrence of each repeating unit enclosed in parentheses with s1 or s2 is arbitrary in the formula.] The fluorine atom-containing silane compound according to claim 1, wherein the fluorine atom is a group represented by the formula:

3. R Ｆ are each independently a group having the formula: -(OC ６ F １２ ) ａ１ -(OC ５ F １０ ) ｂ１ -(OC ４ F ８ ) ｃ１ -(OC ３ R Ｆａ ６ ) ｄ１ -(OC ２ F ４ ) ｅ１ -(OCF ２ ) ｆ１ - [In the formula: a1, b1, c1, d1, e1, and f1 each independently represent an integer of 0 to 200, and the sum of a1, b1, c1, d1, e1, and f1 is 1 or more; The order of the repeating units enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula; R Ｆａ is independently in each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom.

3. The fluorine atom-containing silane compound according to claim 1, wherein the fluorine atom is a group represented by the formula:

4. R Ｆ are each independently represented by the following formula (f11), (f12), (f13), (f14), (f15) or (f16): -(OC ３ F ６ ) ｄ１ -(OC ２ F ４ ) ｅ１ - (f11) [In the formula: d1 is an integer from 1 to 200; e1 is 0 or 1. -(OC ４ F ８ ) ｃ１ -(OC ３ F ６ ) ｄ１ -(OC ２ F ４ ) ｅ１ -(OCF ２ ) ｆ１ - (f12) [In the formula: c1 and d1 each independently represent an integer of 0 to 30; e1 and f1 each independently represent an integer of 1 or more and 200 or less; the sum of c1, d1, e1, and f1 is 2 or greater; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c1, d1, e1, or f1 in the formula is arbitrary. -(R ７１ -R ７２ ) ｇ１ -R ７３ - (f13) [In the formula: R ７１ is OCF ２ or O.C. ２ F ４ and R ７２ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups; R ７３ is a single bond or OCF ２ , O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups selected from these groups; g1 is an integer from 2 to 100. -(R ７１ -R ７２ ) ｇ１ -R ｒ -(R ７２’ -R ７１’ ) ｇ１’ - (f14) [In the formula: R ７１ is OCF ２ or O.C. ２ F ４ and R ７２ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups; R ７１’ is OCF ２ or O.C. ２ F ４ and R ７２’ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups; g1 is an integer from 2 to 100; g1' is an integer from 2 to 100; R ｒ is the following group: 【Chemistry 2】 (In the formula, * indicates the bonding position.) ]; -(OC ６ F １２ ) ａ１ -(OC ５ F １０ ) ｂ１ -(OC ４ F ８ ) ｃ１ -(OC ３ F ６ ) ｄ１ -(OC ２ F ４ ) ｅ１ -(OCF ２ ) ｆ１ - (f15) [In the formula: e1 is an integer of 1 or more and 200 or less, a1, b1, c1, d1, and f1 are each independently an integer of 0 or more and 200 or less, the sum of a1, b1, c1, d1, e1, and f1 is at least 1, and the order of the repeating units enclosed in parentheses after a1, b1, c1, d1, e1, or f1 is arbitrary in the formula.] or -(OC ６ F １２ ) ａ１ -(OC ５ F １０ ) ｂ１ -(OC ４ F ８ ) ｃ１ -(OC ３ F ６ ) ｄ１ -(OC ２ F ４ ) ｅ１ -(OCF ２ ) ｆ１ - (f16) [In the formula: f1 is an integer of 1 or more and 200 or less, a1, b1, c1, d1, and e1 are each independently an integer of 0 or more and 200 or less, the sum of a1, b1, c1, d1, e1, and f1 is at least 1, and the order of the repeating units enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula.] 3. The fluorine atom-containing silane compound according to claim 1, wherein the fluorine atom is a group represented by the formula:

5. R Ｓｉ is expressed by the formula (S1): 【Transformation 3】 [In the formula: R ａ１ are each independently -Z １ -SiR ４１ ｒ１ R ４２ ｒ２ R ４３ ｒ３ and Z １ are each independently an oxygen atom or a divalent organic group; R ４１ are each independently -Z １’ -SiR ４１’ ｒ１’ R ４２’ ｒ２’ R ４３’ ｒ３’ and Z １’ are each independently an oxygen atom or a divalent organic group; R ４１’ are each independently -Z １” -SiR ４１” ｒ１” R ４２” ｒ２” and Z １” are each independently an oxygen atom or a divalent organic group; R ４１” are each independently a hydroxyl group or a hydrolyzable group; R ４２” are each independently a hydrogen atom or a monovalent organic group; Each r1" is independently an integer from 0 to 3; Each r2" is independently an integer from 0 to 3; R ４２’ are each independently a hydroxyl group or a hydrolyzable group; R ４３’ are each independently a hydrogen atom or a monovalent organic group; Each r1' is independently an integer of 0 to 3; Each r2' is independently an integer of 0 to 3; Each r3' is independently an integer of 0 to 3; R ４２ are each independently a hydroxyl group or a hydrolyzable group; R ４３ are each independently a hydrogen atom or a monovalent organic group; Each r1 is independently an integer of 0 to 3; Each r2 is independently an integer of 0 to 3; Each r3 is independently an integer of 0 to 3; R ｂ１ are each independently a hydroxyl group or a hydrolyzable group; R ｃ１ are each independently a hydrogen atom or a monovalent organic group; Each k1 is independently an integer of 0 to 3; Each l1 is independently an integer from 0 to 3; Each m1 is independently an integer of 0 to 3; However, in formula (S1), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group.] The fluorine atom-containing silane compound according to claim 1 or 2, represented by the formula:

6. Z １ are each independently C １－６ Alkylene group, -(CH ２ ) ｚ１ -O-(CH ２ ) ｚ２ - or - (CH ２ ) ｚ３ -phenylene-(CH ２ ) ｚ４ - and; 6. The fluorine atom-containing silane compound according to claim 5, wherein z1 to z4 each independently represent an integer of 0 to 6.

7. A composition comprising the fluorine atom-containing silane compound according to claim 1 or 2.

8. An article having a substrate and a layer formed on the surface of the substrate from the composition of claim 7.

9. Formula (B31) or Formula (B41): 【Chemistry 4】 By adding a methylenylating reagent to a compound represented by formula (B1) or formula (B2): 【Transformation 5】 forming a compound represented by A method for producing a compound comprising: [In the formula: R Ｆ１ is Rf １ -R Ｆ -O ｑ - and; R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ - and; Rf １ is a C optionally substituted by one or more fluorine atoms １－１６ is an alkyl group; Rf ２ is a C optionally substituted by one or more fluorine atoms １－６ an alkylene group; R Ｆ are each independently a divalent fluorine atom-containing group; p is 0 or 1; Each q is independently 0 or 1.

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